Reaction product, process for the production thereof, electrophotographic photoconductor using the reaction product, electrophotographic apparatus using the photoconductor, and process cartridge for electrophotographic apparatus

ABSTRACT

[Problem] To provide a novel reaction product useful as an organic photoconductive material for electrophotographic photoconductors.  
     [Means for Solution] A product obtainable by reacting (i) a nitrile derivative, (ii) a phthalonitrile derivative or a 1,3-diiminoisoindoline derivative and, if necessary, (iii) a metal or a metal-containing compound.

DETAILED DESCRIPTION OF THE INVENTION

[0001] 1. Technical Field to which the Invention Belongs

[0002] The present invention relates to a novel reaction product, to apigment comprising the reaction product, to a process of producing same,to an electrophotographic photoconductor using such a reaction product,to an electrophotographic apparatus having such an electrophotographicphotoconductor, and to a process cartridge for such anelectrophotographic apparatus.

[0003] 2. Prior Art

[0004] Conventionally, the photoconductive material for use in theelectrophotographic process is roughly divided into two groups, that is,an inorganic photoconductive material and an organic photoconductivematerial. The above-mentioned electrophotographic process is one of theimage forming processes, through which the surface of the photoconductoris charged uniformly in the dark to a predetermined polarity, forinstance, by corona charge. The uniformly charged photoconductor isexposed to a light image to selectively dissipate the electric charge ofthe exposed area, so that a latent electrostatic image is formed on thephotoconductor. The thus formed latent electrostatic image is developedinto a visible image by use of a toner comprising a coloring agent suchas a dye or pigment, and a polymeric material. Such anelectrophotographic process is called “Carlson process”.

[0005] The photoconductor employing the organic photoconductive materialis advantageous over that employing the inorganic photoconductivematerial with respect to the degree of freedom in the wave range of thelight to be employed, and the film-forming properties, flexibility,transparency, productivity, toxicity, and manufacturing cost of thephotoconductor. In light of the above-mentioned advantages, most of thecurrent photoconductors employ the organic photoconductive material. Thephotoconductor which is repeatedly operated by the above-mentionedelectrophotographic process or the like is required to exhibit excellentelectrostatic properties, more specifically, excellent photosensitivity,acceptance potential, retentivity of charge, potential stability,residual potential and spectral sensitivity.

[0006] In recent years, the development of data processing apparatusemploying the above-mentioned electrophotographic process is remarkable.In particular, there is a remarkable improvement in the printing qualityand the reliability of the digital printer which is capable of recordingdata by digital recording method, to be more specific, converting thedata into digital signals and recording the data using a light. Such adigital recording system is applied not only to the printer, but also tothe copying machine. Thus, the digital copying machine is activelydeveloped. It is supposed that the demand for the digital copyingmachine will further increase in line with the addition of various dataprocessing functions.

[0007] The photoconductor designed for the above-mentioned digitalrecording system is required to have special characteristics which aredifferent from those required for the conventional analogue recordingsystem. For instance, semiconductor laser (LD) or light emitting diode(LED) is widely employed as a light source for the digital recordingsystem because of its compactness, cheapness and high reliability. Thewave range of the currently used LD is within the near infrared region,while the wavelength of the currently used LED is 650 nm or more.Therefore, the electrophotographic photoconductors for use with theabove-mentioned digital recording system are required to show sufficientsensitivity in the wavelength range from the visible region to the nearinfrared region. In light of the above-mentioned sensitivity, asquarylium dye (Japanese Laid-Open Patent Applications 49-105536 and58-21416), a triphenylamine trisazo pigment (Japanese Laid-Open PatentApplication 61-151659), and a phthalocyanine pigment (Japanese Laid-OpenPatent Applications 48-34189 and 57-14874) are proposed as thephotoconductive materials for use in the digital recording.

[0008] In particular, the phthalocyanine pigment, that is, atitanyltetraazaporphyrin compound, can show absorption andphotosensitivity in the relatively long wavelength range. In addition, avariety of phthalocyanine pigments can be obtained according to the kindof central metal or the type of crystalline form. Therefore, researchand development of this type of phthalocyanine pigment has been activelyconducted to obtain the improved photoconductive material for use withthe digital recording. Examples of the conventional phthalocyaninepigments capable of showing good sensitivity include ε-type copperphthalocyanine, X-type metal-free phthalocyanine, τ-type metal-freephthalacyanine, vanadyl phthalocyanine, and titanyl phthalocyanine. Tobe more specific, titanylphthalocyanine pigments with high sensitivityare proposed in Japanese Laid-Open Patent Applications 64-17066,3-128973 and 5-98182. Those titanylphthalocyanine pigments exhibitmaximum absorption in the wavelength range of 700 to 860 nm, so thatthey can show remarkably high sensitivity with respect to thesemiconductor laser beam. It is also known to be effective for thepurpose of obtaining phthalocyanine pigments with specific crystalstructures to treat the phthalocyanine pigments with an acid, an organicsolvent or water (Japanese Laid-Open Patent Applications 145550).Japanese Laid-Open Patent Applications Nos. 8-6050, 8-283599 and2-269776 disclose a method of treating titanyl phthalocyanines withtrihaloacetic acid.

[0009] However, when each of the above-mentioned titanylphthalocyaninepigments is employed in the electrophotographic photoconductor, therestill remain a lot of practical problems, for example, decline incharging performance due to fatigue, and an increase in temperature- andhumidity-dependence of the charging characteristics although thesensitivity is sufficient [Y. Fujimaki, Proc. IS&T's 7th InternationalCongress on Advances in Non-Impact Printing Technologies, 1,269 (1991);K. Daimon et al.; J. Imaging Sci. Technol., 40,249 (1996)].

[0010] With regard to other tetraazaporphyrin derivatives, JapanesePatent Publication No. 2-39160, 3-27111,4-283581 and 4-113361 disclosethat pigments with asymmetric scheletons or mixed pigments such as amixture of a phthalocyanine with a phthalocyanine-nitrogen orphthalocyanine-sulfur analogue is effective as the photoconductivematerial.

[0011] When these pigments are used for an electrophotographicphotoconductor, the sensitivity in the visible light and near infraredrange, charging characteristics and resistance to repeated use are stillunsatisfactory.

[0012] Problems to be Solved by the Invention

[0013] It is an object of the present invention to remove the drawbacksof the photoconductive material in the conventional electrophotographicphotoconductors and to provide a novel reaction product useful as anorganic photoconductive material for electrophotographicphotoconductors, a process of producing such a reaction product, anelectrophotographic photoconductor containing such a reaction product,an electrophotographic machine using such a photoconductor and a processcartridge for an electrophotographic machine.

[0014] Means for Solving the Problems

[0015] The present inventors have made an earnest study with a viewtoward solving the above problems and have found that a crystallinereaction product capable of being obtained by reaction of (i) a nitrilederivative of the formula (1) shown below with (ii) a phthalonitrilederivative of the formula (2) shown below or a 1,3-diiminoisoindolinederivative of the formula (3) shown below and, if necessary, with (iii)a metal or a metal-containing compound shows excellent charge generatingproperties and excellent electrophotographic characteristics. Thepresent invention is based on this finding.

[0016] In accordance with the present invention, there is provided anamorphous reaction product having charge generating properties andcapable of being obtained by reacting a nitrile derivative of thegeneral formula (1) shown below with a phthalonitrile derivative of thegeneral formula (2) shown below.

[0017] In accordance with the present invention, there is also provideda crystalline reaction product having charge generating properties andcapable of being obtained by reacting a nitrile derivative of thegeneral formula (1) shown below with a phthalonitrile derivative of thegeneral formula (2) below and with a metal or a metal compound.

[0018] In accordance with the present invention, there is furtherprovided a crystalline reaction product having charge generatingproperties and capable of being obtained by reacting a nitrilederivative of the general formula (1) shown below with a1,3-diiminoisoindoline derivative of the formula (3) shown below.

[0019] In accordance with the present invention, there is furtherprovided a crystalline reaction product having charge generatingproperties and capable of being obtained by reacting a nitrilederivative of the general formula (1) shown below with a1,3-diiminoisoindoline derivative of the formula (3) shown below andwith a metal or a metal compound.

[0020] In accordance with the present invention, there is provided anamorphous reaction product capable of being obtained by reacting anitrile derivative of the general formula (1) shown below with aphthalonitrile derivative of the general formula (2) below.

[0021] In accordance with the present invention, there is furtherprovided an amorphous reaction product capable of being obtained byreacting a nitrile derivative of the general formula (1) shown belowwith a phthalonitrile derivative of the general formula (2) shown belowand with a metal or a metal compound.

[0022] In accordance with the present invention, there is furtherprovided an amorphous reaction product capable of being obtained byreacting a nitrile derivative of the general formula (1) shown belowwith a 1,3-diiminoisoindoline derivative of the formula (3) shown below.

[0023] In accordance with the present invention, there is furtherprovided an amorphous reaction product capable of being obtained byreacting a nitrile derivative of the general formula (1) shown belowwith a 1,3-diiminoisoindoline derivative of the formula (3) shown belowand with a metal or a metal compound.

[0024] In accordance with the present invention, there is furtherprovided a process for the production of a reaction product having astrong diffraction peak at a Bragg angle 2θ±0.2° of 27.2° but having nodiffraction peak at a Bragg angle 2θ±0.2° of in the range of 4°-10° in aCuK_(α) X-ray diffraction pattern thereof, characterized in that areaction product having a strong diffraction peak at a Bragg angle2θ±0.2° of 27.2° and having weak diffraction peak at a Bragg angle2θ±0.2° of in the range of 4°-10° in a CuK_(α) X-ray diffraction patternthereof or the above amorphous reaction product is subjected to acrystal conversion treatment using at least one solvent selected fromorganic solvents, acids and water.

[0025] In accordance with the present invention, there is furtherprovided a pigment characterized in that the pigment comprises the abovecrystalline reaction product having charge generating properties.

[0026] In accordance with the present invention, there is furtherprovided an electrophotographic photoconductor comprising anelectroconductive support and a photoconductive layer provided thereon,characterized in that the photoconductive layer comprises the abovepigment.

[0027] In accordance with the present invention, there is furtherprovided an electrophotographic machine comprising charging means,exposing means, developing means, transfer means, cleaning means, chargeremoving means and an electrophotographic photoconductor, characterizedin that the above electrophotographic photoconductor is mounted as theelectrophotographic photoconductor.

[0028] In accordance with the present invention, there is furtherprovided a process cartridge for an electrophotographic machinecomprising charging means and an electrophotographic photoconductor,characterized in that the above electrophotographic photoconductor ismounted as the electrophotographic photoconductor.

[0029] In the above formulas (1)-(3), R₁-R₅ stand, independently fromeach other, for a hydrogen atom, a halogen atom, an aliphatichydrocarbyl group which may have a substituent, an aromatic group whichmay have a substituent, a hydrocarbyloxy group which may have asubstituent, a nitro group or a cyano group and n is an integer of 1 or2, with the proviso that two of R₂-R₅ may link to each other to form aring.

EMBODIMENTS OF THE INVENTION

[0030] A first reaction product according to the present invention is ametal-free reaction product capable of being obtained by reacting (i) anitrile derivative of the above general formula (1) with (ii) aphthalonitrile derivative of the above general formula (2) or a1,3-diiminoisoindoline derivative of the above formula (3).

[0031] A second reaction product according to the present invention is ametal-containing reaction product capable of being obtained by reacting(i) a nitrile derivative of the above general formula (1) with (ii) aphthalonitrile derivative of the above general formula (2) or a1,3-diiminoisoindoline derivative of the above formula (3) and (iii)with a metal or a metal compound.

[0032] In the above formulas (1)-(3), R₁-R₅ stand, independently fromeach other, for a hydrogen atom, a halogen atom, an aliphatichydrocarbyl group, an aromatic group, a hydrocarbyloxy group, a nitrogroup or a cyano group, with the proviso that two of R₂-R₅ may link toeach other to form a ring.

[0033] The aliphatic hydrocarbyl group has a number of carbon atoms of1-20, preferably 1-10 and may be a chain or cyclic hydrocarbyl group.The chain hydrocarbyl groups includes alkyl and alkenyl groups.Preferred chain aliphatic hydrocarbyl groups include alkyl groups having1-20 carbon atoms, preferably 1-4 carbon atoms. The cyclic hydrocarbylgroups may be cycloalkyl groups having 5-20 carbon atoms, preferably6-10 carbon atoms.

[0034] A substituent may be bonded to the aliphatic hydrocarbyl group.Such a substituent is inert to the reaction used in the presentinvention. The substituents may include halogen atoms, alkoxyl groupshaving 1-6 carbon atoms, a nitro group and a cyano group.

[0035] The above aromatic group has an aromatic nucleus of a carbon ringor a hetero ring. The aromatic group having a carbon ring may be asingle ring (benzene ring), a polycyclic condensed ring (naphthalenering, pyrene ring, fluorene ring, anthracene ring, chrysene ring, etc.)or a polycyclic chain ring (biphenyl, terphenyl, etc.). The aromaticgroup including a hetero ring may be a heteroaromatic group having atleast one of hetero atoms such as a nitrogen atom, an oxygen atom and asulfur atom.

[0036] Such aromatic groups may include those having 1-20, preferably1-10 atoms that constitute the ring. Illustrative of hetero rings arethiophene ring, benzothiophene ring, thianthrene ring, furan ring,benzofuran ring, carbazol ring, pyridine ring, pyrazine ring andpyrrolidine ring.

[0037] A substituent may be bonded to the aromatic group. Such asubstituent is inert to the reaction used in the present invention. Thesubstituents may include halogen atoms, alkyl groups having 1-6 carbonatoms, alkoxyl groups having 1-6 carbon atoms, a nitro group, a cyanogroup, a phenyl group and a naphthyl group.

[0038] The above hydrocarbyloxy group may be an aliphatic hydrocarbyloxygroup or an aromatic hydrocarbyloxy group. The aliphatic hydrocarbyloxygroup may be a linear alkoxyl group having 1-20 carbon atoms, preferably1-10 carbon atoms, or a cyclic alkoxyl group having 1-20 carbon atoms,preferably 1-10 carbon atoms. The aromatic hydrocarbyloxy group may bean alryloxy group having 6-18 carbon atoms, preferably 6-12 carbonatoms, or an arylalkoxyl group having 7-18 carbon atoms, preferably 7-12carbon atoms.

[0039] A substituent may be bonded to the hydrocarbyloxy group. Such asubstituent is inert to the reaction used in the present invention. Thesubstituents may include halogen atoms, a nitro group and a cyano group.

[0040] Examples of halogen atoms include iodine, bromine, chlorine andfluorine. Examples of aliphatic hydrocarbyl groups which may have asubstituent include methyl group, ethyl group, n-propyl group,iso-propyl group, tert-butyl group, sec-butyl group, n-butyl group,iso-butyl group, trifluoromethyl group, 2-cyanoethyl group.

[0041] Examples of aromatic groups which may have a substituent includephenyl group, naphthyl group, biphenylyl group, terphenylyl group,pyrenyl group, fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenylgroup, anthryl group, triphenylenyl group, chrysenyl group,fluorenylidenephenyl group, 5H-dibenzo[a,d]cycloheptenylidenephenylgroup, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group,naphthylmethyl group, thienyl group, benzothienyl group, furyl group,benzofuranyl group, carbazolyl group, pyridyl group, pyridinyl group,pyrrolidyl group and oxazolyl group.

[0042] Examples of hydrocarbyloxy groups which may have a substituentinclude methoxy group, ethoxy group, n-propoxy group, iso-propoxy group,n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group,2-hydroxyethoxy group, 2-cyanoethoxy group, benzyloxy group,4-methylbenzyloxy group and trifluoromethoxy group.

[0043] The metal may be an alkali metal or an alkaline earth metal.Illustrative of suitable metals are Mg, Li and Na.

[0044] The metal compound may be an alkali metal compound, an alkalineearth metal compound or a transition metal compound. Especially,compounds of metals selected from those belonging to Groups IB, IIB,IIA, IVA, IVB, VB, VIB, VIIB and VIII of the Short Periodic Table areincluded in the metal compounds.

[0045] Illustrative of suitable metal compounds are compounds having ametal such as Na, Li, Cu, Ti, Mg, Co, Mn, Pb, V, Fe, Zn, Ge, Sn, Ni, Al,Ga, Mo or In.

[0046] Any kind of conventional metal compounds may be used for thepurpose of the present invention. Metal halides and metal alkoxides aresuitably used. Examples of the metal compounds may include metal halidessuch as TiCl₄, CoCl₂, CuCl₂, CuCl, InCl₃, InBr₃, AlCl₃, GaCl₂ and VCl₃,and metal alkoxides such as Ti(OBu)₄ and Mg(OEt)₂.

[0047] Shown in Tables 1 and 2 are examples of reaction productsaccording to the present invention illustrated in terms of rawmaterials. The reaction products those obtained by reaction of (i) thecompound (1) (nitrile derivative) shown below with the compound (2)(phthalonitrile derivative) shown below and those obtained by reactionof (i) the compound (1) shown below with (ii) the compound (2) shownbelow and with (iii) metals or metal-containing compounds. In Tables 1and 2, R₁ and n correspond to R₁ and n of the compound (1) shown below,while R₂-R₅ correspond to R₂-R₅ of the compound (2) shown below. TABLE 1(1)

(2)

Metal or metal- Product containing No. R₁ R₂ R₃ R₄ R₅ compound 1-A Ph HH H H CuCl n 1-B Ph H H H H Ti(OBu)₄ 1 (1,4-) 1-C Ph H H H H Mg 1 (1,4-)1-D Ph H H H H VCl₃ 1 (1,4-) 1-E Ph H H H H AlCl₃ 1 (1,4-) 1-F Ph H H HH AlCl₃ 1 (1,3-) 1-G Ph H H H H AlCl₃ 2 (1,4-) 1-H Ph H H H H AlCl₃ 2(1,3-) 1-I Ph H H H H GaCl₂ 2 (1,2-) 1-J Ph H H H H GaCl₂ 1 (1,4-) 1-KPh H H H H GaCl₂ 1 (1,3-) 1-L Ph H H H H CoCl₂ 2 (1,4-) 1-M Ph H H H HInCl₃ 1 (1,4-) 1-N Ph H H H H InBr₃ 1 (1,3-) 2-A H H H H H CuCl 2 (1,4-)2-B H H H H H Ti(OBu)₄ 2 (1,3-) 2-C H H H H H Mg 1 (1,4-) 2-D H H H H HTi(OBu)₄ 1 (1,4-) 3-A Ph F F F F CuCl 1 (1,3-) 3-B Ph F F F F Ti(OBu)₄ 1(1,4-) 3-C Ph F F F F Mg 1 (1,3-) 3-D Ph F F F F VCl₃ 1 (1,4-) 4-A F F FF F CuCl₂ 1 (1,4-) 4-B F F F F F Ti(OBu)₄ 1 (1,4-) 4-C F F F F F Mg 1(1,4-) 4-D F F F F F VCl₃ 1 (1,3-)

[0048] TABLE 2 Metal or metal- Product containing No. R₁ R₂ R₃ R₄ R₅compound n  5A Me H H H H Ti(OBu)₄ 1 (1,4-)  6A Me F F F F Ti(OBu)₄ 1(1,4-)  7A Ph H

H Ti(OBu)₄ 1 (1,4-)  8A H H

H TiCl₄ 1 (1,4-)  9A H H Me H H Ti(OBu)₄ 1 (1,4-) 10A Ph H Me H HTi(OBu)₄ 1 (1,4-) 12-A Ph H H H H — 1 (1,4-) 12-B Ph H H H H — 1 (1,3-)12-C Ph H H H H — 2 (1,4-) 12-D Ph H H H H — 2 (1,3-) 12-E Ph H H H H —2 (1,2-) 12-F Ph H H H H — 1 (1,4-) 12-G Ph H H H H — 1 (1,3-) 12-H Ph HH H H — 2 (1,4-) 12-I H H H H H — 2 (1,3-) 12-J H H H H H — 1 (1,4-)12-K Ph F F F F — 1 (1,4-) 12-L Ph F F F F — 1 (1,3-) 12-M F F F F F — 1(1,4-) 12-N F F F F F — 1 (1,3-) 12-O F F F F F — 1 (1,4-) 12-P Me H H HH — 1 (1,4-) 12-Q Me F F F F — 1 (1,4-) 12-R Ph H

H — 1 (1,4-) 12-S H H

H — 1 (1,4-) 12-T H H Me H H — 1 (1,4-) 12-U Ph H Me H H — 1 (1,4-)

[0049] The reaction products shown in Tables 1 and 2 may be obtained byreacting the above nitrile derivative with the above phthalonitrilecompound and, if necessary, with a metal or a metal-containing compoundwithout using a solvent or in the presence of a solvent. The reactiontemperature is generally from room temperature to 300° C., especiallyfrom 40° C. to 200° C. The use of such a temperature is preferred forreasons of reduced by-products and from the standpoint of yield.

[0050] The solvent may be a halogenated hydrocarbon such asα-chloronaphthalene, dichlorobenzene or trichlorobenzene, an alcoholsuch as pentanol or octanol, an amine such as N,N-dimethylformamide orN-methylpyrrolidone, or an aromatic hydrocarbon such as benzene, tolueneor nitrobenzene.

[0051] The amount of the phthalonitrile derivative (compound 2) is6-4000 moles, preferably 6-1,600 moles, more preferably 6-800 moles, permole of the nitrile derivative (compound 1). The amount of the metal ormetal compound is 0.001-100 moles, preferably 0.1-10 moles, morepreferably 0.25-1.0 mole, in terms of metal, per mole of the nitrilederivative.

[0052] When a solvent is used, the amount thereof is 50-3000 parts byweight, preferably 200-1500 parts by weight, per 100 parts by weight ofthe nitrile derivative.

[0053] The reaction product according to the present invention may be aproduct obtained by reacting (i) a nitrile derivative of the generalformula (1) shown below with (ii) a 1,3-diiminoisoindoline derivative ofthe general formula (3) shown below or a product obtained by reacting(i) a nitrile derivative of the general formula (1) shown below with(ii) a 1,3-diiminoisoindoline derivative of the general formula (3)shown below in the presence of (iii) a metal or a metal compound.

[0054] The reaction of the nitrile derivative with the1,3-diiminoisoindoline derivative can be performed in the same manner asthat of the reaction between the nitrile derivative and thephthalonitrile derivative. The reaction temperature is especially70-300° C., preferably 100-140° C. The amount of the1,3-diiminoisoindoline derivative is 6-4000 moles, preferably 6-1600moles, more preferably 6-800 moles, per mole of the nitrile derivative.

[0055] The phthalonitrile compound (2) and the 1,3-diiminoisoindoline(3) may be obtained by a known method disclosed in “Phthalocyanine,Chemistry and Function”by Shirai and Kobayashi. Some of them are alsocommercially available.

[0056] The nitrile compound (1) may be prepared according to thefollowing reaction:

[0057] wherein n is an integer of 1 or 2.

[0058] The above reaction may be carried out with heating generally inthe absence of a solvent or in the presence of a solvent such as analcohol, e.g. ethanol, butanol, pentanol or octanol, an aromatichydrocarbon, e.g. benzene, toluene or nitrobenzene, a halogenatedhydrocarbon, e.g. □-chloronaphthalene, dichlorobenzene ortrichlorobenzene, an acidic solvent, e.g. acetic acid, or an amine, e.g.N,N-dimethylformamide or 1-methyl-2-pyrrolidinone. For reasons ofimproving reaction yield and solubility of reaction raw materials, it ispreferred that the reaction be performed in the presence of an acidcatalyst such as acetic acid, sulfuric acid or hydrochloric acid. Theabove reaction is performed at a temperature of generally from roomtemperature to 300° C. The use of a reaction temperature from 100° C. to180° C. is preferred from the standpoint of yield.

[0059] The reaction of the nitrile compound (1) with the naphthonitrilecompound (2) or 1,3-diiminoisoindoline (3) may be carried out in thepresence of an amine catalyst such as urea, formamide or1,8-diazabicyclo[5,4,0]-undecene (DBU). The amine catalyst may be usedin an amount of 0.1-100 moles, preferably 0.1-5 moles, per mole of thenitrile derivative.

[0060] The product obtained by the reaction of the nitrile compound ofthe above general formula (1) with the phthalonitrile compound of theabove general formula (2) or 1,3-diiminoisoindoline of the above generalformula (3) and, if necessary, with the metal or metal-containingcompound is a solid at room temperature. The color is green to dark bluedepending upon the composition of the product and is suitable as anorganic pigment.

[0061] The reaction product according to the present invention may becrystalline solid. The crystalline solid does not have a melting pointbut decomposes at 400° C. or more to cause reduction of mass. Thecrystal structure of the crystalline solid may be converted, if desired,into another crystal structure by a crystal converting treatment.

[0062] As a method of converting crystal structure to obtain a reactionproduct having a different crystal structure, conventional methods, suchas an acid treatment, a solvent treatment, a mechanical treatment, aheat treatment, a milling treatment and a combination of thesetreatments, may be used.

[0063] In the acid treatment, a solid (reaction product) is dissolved inan acid, such as sulfuric acid, trichloroacetic acid or trifluoroaceticacid, or a mixture of such an acid with an organic solvent preferably ata temperature of 0° C. to room temperature. The solution thus obtainedis then added dropwise to ice water, water or an organic solvent or amixed organic solvent in which the reaction product is insoluble orhardly soluble, so that solids are precipitated. The solid product isseparated by filtration or the like method to obtain a reaction product.

[0064] In the solvent treatment, a solid (reaction product) is suspendedwith stirring in an organic solvent, water or a mixture thereof at roomtemperature or at an elevated temperature. The organic solvent may be,for example, an aromatic hydrocarbon such as benzene, toluene,dichlorobenzene or nitrobenzene, an alcohol such as methanol, ethanol,n-propanol, n-butanol or n-pentanol, a ketone such as acetone,cyclohexanone or methyl ethyl ketone, an ether such as n-butyl ether,ethylene glycol n-butyl ether or tetrahydrofuran, an amine such asN,N-dimethylformamide, N-methylpyrrlidone or quinoline, an ester such asmethyl acetate, ethyl acetate or n-butyl acetate, or anitrogen-containing solvent such as 2-pyrrolidinone,1-methyl-2-pyrrolidinone, 5-methyl-2-pyrrolidinone,1,5-dimethyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone,2-imidazolidinone or 1-(2-hydroxyethyl)-2-imidazolidinone.

[0065] The amount of the organic solvent is desirably at least 5 times,more preferably 5-100 times, the volume of the solid of the reactionproduct for reasons of facilitating stirring and of obtaining uniformcrystals. When one or more organic solvents are used by themselves, thesolvent treatment is generally performed at a temperature of 250° C. orless. When water and an organic solvent are used for the solventtreatment, they can be mixed with the reaction product in any desiredorder. Water and an organic solvent may be mixed in a reactor so thatthe reaction product can be added to the organic solvent in which wateris dissolved in a saturated amount in the initial stage and is surelypresent. The reaction product which has been subjected to the above acidtreatment may be subsequently treated with an organic solvent or amixture of two or more organic solvents, as such without being dried, atroom temperature or an elevated temperature. The temperature at whichthe heat treatment is carried out is 50-200° C., preferably 50-150° C.The treatment time is not specifically limited but is desired to be suchthat the mixture can be sufficiently stirred homogeneously. The reactionproduct subjected to the above acid treatment may be dried before thesolvent treatment.

[0066] In the milling treatment, the reaction product is treated atambient temperature or an elevated temperature with a milling devicesuch as sand mill or ball mill using glass beads, steel beads or aluminaballs. The milling treatment may be carried out using the above millingmedium together with a solvent.

[0067] The reaction product according to the present invention can be anamorphous solid. The amorphous solid also decomposes at 400° C. or more.

[0068] As the method of obtaining an amorphous reaction product, theremay be mentioned, for example, an acid treatment and a mechanicaltreatment. One acid treatment is an acid paste method in which a solidreaction product is added little by little to an acid, such as sulfuricacid, trichloroacetic acid or trifluoroacetic acid, at a temperature ofnot higher than room temperature, preferably 0° C. to room temperature,with stirring, to dissolve the solid therein. The solution thus obtainedis then added dropwise to ice, water or an organic solvent or a mixedorganic solvent in which the solid product is not or scarcely soluble,thereby precipitating the reaction product which is thereafter collectedby filtration. It is preferred that the above solution or dispersion beadded to ice or ice water, especially ice water. Further, it ispreferred that the above solution be added to vigorously stirred icewater for quickly diffusing the solution into the ice water.

[0069] The mechanical treatment may be a milling treatment in which thesolid product is treated with a milling device such as sand mill or ballmill using glass beads, steel beads or alumina balls at room temperatureor an elevated temperature.

[0070] Whether or not the product is amorphous can be confirmed by adiffraction pattern in X-ray analysis. When the product is amorphous, nosharp peaks are present in the X-ray diffraction pattern using CuK_(α)ray. In the present specification, the term “sharp peak” is intended torefer to a peak having a half-width value of not greater than 1°. Thus,a product which does not provide, in X-ray analysis thereof, an X-raydiffraction pattern having a diffraction peak of not greater than 1° isan amorphous product.

[0071] A product obtained by the reaction of the nitrile compound (1)with the phthalonitrile compound (2) and, optionally, with the metal ormetal-containing compound in the presence of an organic solvent isgenerally a crystalline product. Thus, when the crystalline product isto be converted into a product having a different crystal structure, itis preferred that the reaction product be first subjected to an acidtreatment for the conversion of the crystalline product into amorphousproduct and then to a solvent treatment, because the conversion of thecrystal structure can be easily performed.

[0072] For the production of a reaction product having various differentcrystal structures, it is effective that a crystalline or amorphousproduct be subjected a treatment with an organic solvent (as describedabove) with stirring at room temperature or an elevated temperature,preferably at 50° C. or less. An acid treatment is also effective. Inthe acid treatment, the reaction product is dissolved little by littlein an acid such as sulfuric acid, trichloroacetic acid, trifluoroaceticacid or a mixture of such an acid with an organic solvent at atemperature of 0° C. to room temperature. The solution thus obtained isthen added dropwise to water, ice water, ice or an organic solvent or amixed organic solvent in which the product is insoluble or hardlysoluble, so that the reaction product is precipitated. The treatedproduct is separated by filtration.

[0073] It is possible to obtain a reaction product having differentcrystal structures by controlling the treatment conditions, such as kindof solvent, treatment time and treatment temperature, of the solventtreatment or acid treatment. The reaction product having differentcrystal structures can be confirmed by a diffraction pattern in X-raydiffraction analysis.

[0074] The crystalline reaction product according to the presentinvention is featured by having charge generating properties. While areaction product having any crystal structure can exhibit chargegenerating properties, it is preferred that the product provide aCuK_(α) X-ray diffraction pattern having strong diffraction peaks at aBragg angle 2θ±0.2° of in the range of 2°-30°, more preferably a CuK_(α)X-ray diffraction pattern having strong diffraction peaks at a Braggangle 2θ±0.2° of 27.2°, most preferably a CuK_(α) X-ray diffractionpattern having strong diffraction peaks at a Bragg angle 2θ±0.2° of27.2° but no diffraction peaks at a Bragg angle 2θ±0.2° of in the rangeof 4°-10°, for reasons of exhibiting excellent charge generatingefficiency and good electrophotographic characteristics.

[0075] The reaction product providing a CuK_(α) X-ray diffractionpattern having strong diffraction peaks at a Bragg angle 2θ±0.2° of27.2° but no diffraction peaks at a Bragg angle 2θ±0.2° of in the rangeof 4°-10° will be described in detail below. The term “a diffractionpattern having no diffraction peaks at a Bragg angle 2θ±0.2° of in therange of 4°-10°” used herein is intended to refer to a CuK_(α), X-raydiffraction pattern which does not have, in a Bragg angle 2θ±0.2° of inthe range of 4°-10°, any peak attributed to crystals, any low intensitypeak with a broad half-width value attributed to fine crystals, and anysuch a low intensity halo (which is not a clear peak) as seen in aglassy state material. When the product has such a peak attributed tocrystals or fine crystals or a halo at a Bragg angle 2θ±0.2° of in therange of 4°-10°, there is a fear the resulting electrophotoconductiveproperties are adversely affected due to a change of the crystalstructure caused during a crystal treatment in an organic solvent orupon lapse of time. Although the cause is not clear, it is inferred thatcrystals or fine crystals which causes a peak or halo at a Bragg angle2θ±0.2° of in the range of 4°-10° serve as a seed crystal to alter thecrystal structures. On the other hand, a reaction product providing adiffraction pattern having no diffraction peaks at a Bragg angle 2θ±0.2°of in the range of 4°-10° has excellent stability and can retain itscrystal structures even when stored in an organic solvent. Thus, acoating liquid for use in coating of a photoconductive layer of anelectrophotographic photoconductor permits long period storage, ensuringreduction in manufacturing costs.

[0076] For the production of a reaction product having no of 4°-10°, itis preferable to use a mixture of trifluoroacetic acid with an organicsolvent, more preferably a mixture of trifluoroacetic acid with achlorine-containing solvent for the treatment of the reaction product.The chlorine-containing organic solvent may be, for example, chloroform,dichloromethane or 1,2-dichloroethane. The mixing ratio of the organicsolvent to the acid is 0.1:99.9 to 99.9:0.1, preferably 0.5:99.5 to99.5:0.5, more preferably 1:9 to 9:1 for reasons of solubility of thereaction product in the mixed liquid and for conversion of the wholereaction product into desired crystals. The product is dissolved littleby little in the mixture of trifluoroacetic acid with achlorine-containing solvent. The solution thus obtained is then addeddropwise to an organic solvent or a mixed organic solvent in which theabove product is insoluble or hardly soluble, so that the reactionproduct is precipitated. While any organic solvent as the above organicsolvent may be used, the use of a mixed solvent containing achlorine-containing and an alcohol is preferred. The chlorine-containingsolvent may be chloroform, dichloromethane or 1,2-dichloroethane, whilethe alcohol may be methanol or ethanol.

[0077] The crystalline reaction product according to the presentinvention has charge generating properties and, hence, is suitably usedas a charge generating material for electrophotographic photoconductors.When the crystalline reaction product is dispersed in a binder and isformed into a film, the film can absorb light of a near infrared region,i.e. a wavelength in the range of 500-700 nm, which corresponds to thewavelength of light emitted from laser diodes (LD). Thus, with the useof the product according to the present invention as a charge generatingmaterial, it is possible to obtain an electrophotographic photoconductorhaving high sensitivity.

[0078] The product according to the present invention can be confirmedby mass spectrometry. For example, when the nitrile derivative A of thefollowing formula (6), the phthalonitrile of the formula (7) andTi(OBu)₄ as a metal-containing compound are reacted, there is obtained areaction product providing a mass spectrum having a peak at 1383±1.

[0079] Thus, the above reaction product would contain the compounds ofthe following formulas (8) and (9). The mass spectrometry of thereaction product gives fragment peaks corresponding to the molecularweight of 1383±1 attributed to the compound (8) and the molecular weightof 576±1 attributed to the compound (9), from which the reaction productaccording to the present invention can be confirmed.

[0080] Additionally, X-ray fluorescent elementary analysis can detect Tiin the reaction product.

[0081] An electrophotographic photoconductor of a single-layered type ora layered type (function-separating type) can be fabricated, using thecrystalline product (pigment) having charge generating propertiesaccording to the present invention alone or in combination with a chargetransport material. To fabricate the electrophotogracphic photoconductorof a single-layered type, a photoconductive layer is provided on anelectroconductive support in such a manner that the solvent-treatedproduct is dispersed in a binder resin singly or together with a chargetransport material. In the case of a layered type (function-separatingtype), a charge generation layer comprising the solvent-treated productis provided on an electroconductive support, and a charge transportlayer comprising a charge transporting material is overlaid on thecharge generation layer. The charge generation layer and the chargetransport layer may be laminated in reversed order.

[0082] An intermediate layer may be provided between the support and thephotoconductive layer for the purpose of improving the adhesion and forenhancing the charge blocking characteristics. Furthermore, a protectivelayer may be provided on the photoconductive layer to improve themechanical durability, such as wear resistance.

[0083] The photoconductive layer may be prepared by dissolving ordispersing the solvent-treated reaction product in a suitable solventoptionally together with a binder, the resulting liquid being appliedand dried.

[0084] As a method for dispersing the crystalline reaction producthaving charge generating properties according to the present invention,there may be mentioned a ball mill, ultrasonic wave or a homomixer. Theapplication of the coating liquid may be by dip coating, blade coatingor spray coating.

[0085] To upgrade the dispersibility of the reaction product in thephotoconductive layer for the preparation of the photoconductive layer,it is preferable that the average particle size of the reaction productbe 2 μm or less more preferably 1 mμ or less. The lower limit of theaverage particle size is preferably 0.01 mμ, because too small aparticle diameter causes aggregation of fine particles, increase of theresistivity of the photoconductive layer, deterioration of sensitivityand durability due to an increase of defective crystallites andlimitation of fine pulverization.

[0086] Specific examples of the solvent which is used to prepare adispersion or solution for the formation of the photoconductive layerinclude N,N-dimethylformamide, toluene, xylene, monochlorobenzene,1-methyl-2-pyrrlidinone, 1,2-dichloroethane 1,1,1-trichloroethane,dichloromethane, 1,1,2 trichloroethane, trichloroethylene,tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketane,cyclohexanone, ethyl acetate, butyl acetate and dioxane.

[0087] Any binder resin that has good electrically insulating propertiesand conventionally used in the preparation of the electrophotographicphotoconductor can be employed for the formation of the photoconductivelayer in the present invention. Specific examples of such a binder resininclude addition polymerization-type resins, polyaddition-type resinsand polycondensation-type resins such as polyethylene, polyvinylbutyral, polyvinyl formal, polystyrene resin, phenoxy resin,polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin,vinyl acetate resin, epoxy resin, polyurethane resin, phenolic resin,polyester resin, alkyd resin, polycarbonate resin, polyamide resin,silicone resin and melamine resin; copolymer resins comprising as therepeating units two or more monomers for use in the above-mentionedresins, for example, electrically insulating resins such as vinylchloride-vinyl acetate copolymer resin, styrene-acrylic copolymer resin,and vinyl chloride-vinyl acetate-maleic anhydride copolymer resin; and apolymeric organic semiconductor such as poly-N-vinylcarbazole. Thesebinder resins may be used alone or in combination.

[0088] The crystalline reaction product (pigment) according to thepresent invention may be used as a mixture with another pigment such asa phthalocyanine pigment according to required characteristics of thephotoconductor.

[0089] The mixing method is not specifically limited and may be carriedout by various suitable methods.

[0090] Examples of such mixing methods include (1a) a method in whichthe reaction product of the present invention is mechanically millingwith a phthalocyanine pigment by a conventional method, (2a) a method inwhich the reaction product of the present invention is mixed with aphthalocyanine pigment using a conventional mixing device such as atumbler for use in mixing powders, (3a) a method in which the reactionproduct of the present invention is mixed with a phthalocyanine pigmentin a suitable organic solvent such as xylene using a mixer, (4a) amethod in which the reaction product of the present invention and aphthalocyanine pigment are added to a binder resin and dispersed using adevice such as ball mill or sand mill, (5a) a method in which thereaction product of the present invention and a phthalocyanine pigmentis dispersed in a binder resin, followed by addition of the reactionproduct or the phthalocyanine pigment, and (6a) a method in which thereaction product of the present invention and a phthalocyanine pigmentare mixed in an inorganic acid such as sulfuric acid, phosphoric acid,acetic acid or an organic acid such as trifluoroacetic acid, followed bycoprecipitation with water or an alkaline substance. The presentinvention is not limited to the above methods.

[0091] The mixing ratio of the product to the phthalocyanine pigment is,in terms of molar ratio, preferably 0.001:99.999 to 99.999:0.001, morepreferably 0.1:99.9 to 99.9:0.1, for reasons of prevention of anincrease in residual potential and a reduction of chargeability duringrepeated use.

[0092] Examples of the phthalocyanine pigment for use in the presentinvention include metal-free phthalocyanine, metal phthalocyanine or amixture thereof. The metal phthalocyanine may be copper phthalocyanine,aluminum phthalocyanine, magnesium phthalocyanine, chlorogalliumphthalocyanine, hydroxygallium phthalocyanine, vanadyl phthalocyanine,titanyl phthalocyanine, chloroindium phthalocyanine, hydroxyindiumphthalocyanine, zinc phthalocyanine, iron phthalocyanine or cobaltphthalocyanine but is not limited to the above.

[0093] The reaction product according to the present invention may bealso used in combination with other pigments than phthalocyanine pigmentas follows: organic pigments, for example, azo pigments such as C.I.Pigment Blue 25 (C.I. 21180), C.I. Pigment Red 41 (C.I. 21200), C.I.Acid Red 52 (C.I. 45100), C.I. Basic Red 3 (C.I. 45210), an azo pigmenthaving a carbazole skeleton (Japanese Laid-Open Patent Application53-95033), an azo pigment having a distyryl benzene skeleton (JapaneseLaid-Open Patent Application 53-133445), an azo pigment having atriphenylamine skeleton (Japanese Laid-Open Patent Application53-132347), an azo pigment having a dibenzothiophene skeleton (JapaneseLaid-Open Patent Application 54-21728), an azo pigment having anoxadiazole skeleton (Japanese Laid Open Patent Application 54-12742), anazo pigment having a fluorenone skeleton (Japanese Laid-Open PatentApplication 54-22834), an azo pigment having a bisstilbene skeleton(Japanese Laid-Open Patent Application 54-17733), an azo pigment havinga distyryl oxadiazole skeleton (Japanese Laid-Open Patent Application54-2129), and an azo pigment having a distyryl carbazole skeleton(Japanese Laid-Open Patent Application 54-14967); indigo pigments suchas C.I. Pigment Blue 16 (C.I. 74100) C.I. Vat Brown 5 (C.I. 73410) andC.I. Vat Dye (C.I. 73030); and perylene pigments such as Algol Scarlet Band Indanthrene Scarlet R (made by Bayer Co. Ltd.). Two or more organicpigments mentioned above may be used.

[0094] In fabrication of a photoconductor using the above layerconstitution and substances, there are preferred ranges for the filmthickness and the amount of the substances. In the case of a functionseparation type (support/charge generation layer/charge transportlayer), a binder is used as required in the charge generation layer. Inthis case, the amount of the reaction product is preferably at least 20%by weight based on the binder and the thickness of the charge generationlayer is preferably in the range of 0.01 to 5 μm. In the chargetransport layer, the amount of the charge transport material ispreferably in the range of 20 to 200 wt % based on the binder and thethickness of the charge transport layer is preferably in the range of 5to 100 μm. The charge transport layer may be formed using ahigh-molecular weight charge transport material alone.

[0095] It is preferred that the charge generation layer contain a chargetransport material for reasons of reducing the residual potential andimproving the sensitivity. The charge transport material is preferablyused in an amount of 20 to 200% by weight based on the binder.

[0096] In the single-layered photoconductive layer, it is preferablethat the amount of the reaction product of the present invention be inthe range of 5 to 95% by weight based on the binder resin for use in thephotoconductive layer. In this case, the thickness of the single-layeredphotoconductive layer is preferably in the range of 10 to 100 μm. When acharge transport material is added to the single-layered photoconductivelayer, it is preferable that the amount of the charge transport materialbe in the range of 30 to 200% by weight based on the binder resin. Therecan be employed a photoconductive layer comprising a high-molecularweight charge transport material and the product according to thepresent invention. In this case, it is preferable that the amount of theproduct be in the range of 5 to 95% by weight based on thehigh-molecular weight charge transport material. In this case, it ispreferable that the thickness of the photoconductive layer be in therange of 10 to 100 μm.

[0097] To improve the chargeability, the photoconductive layer mayfurther comprise a phenol compound, a hydroquinone compound, a hinderedphenol compound, a hindered amine compound, and a compound having ahindered amine and a hindered phenol in a molecule thereof.

[0098] As the electroconductive support, there can be employed ametallic plate, drum or foil made of aluminum, nickel, copper, titanium,gold or stainless steel; a plastic film on which an electroconductivematerial such as aluminum, nickel, copper, titanium, gold, tin oxide orindium oxide is deposited; and a sheet of paper or a plastic film, whichmay be formed in a drum, coated with an electroconductive material.

[0099] An intermediate layer may be provided on the electroconductivesupport. The intermediate layer comprises a resin as the main component.Since the photoconductive layer is provided on the intermediate layer bya coating method using a solvent, it is desirable that the resin for usein the intermediate layer have high resistance against general-purposeorganic solvents. Preferable examples of the resin for use in theintermediate layer include water-soluble resins such as polyvinylalcohol, casein and sodium polyacrylate; alcohol-soluble resins such ascopolymer nylon and methoxymethylated nylon; and hardenable resins withthree-dimensional network such as polyurethane, melamine resin, phenolicresin, alkyd-melamine resin and epoxy resin. The undercoat layer mayfurther comprise finely-divided particles of metallic oxides such astitanium oxide, silica, alumina, zirconium oxide, tin oxide and indiumoxide in order to prevent the occurrence of moire and reduce theresidual potential. Similar to the previously mentioned photoconductivelayer, the intermediate layer can be provided on the electroconductivesupport by coating method, using an appropriate solvent. Further, theintermediate layer for use in the present invention may be preparedusing a coupling agent such as a silane coupling agent, titaniumcoupling agent or chromium coupling agent. Furthermore, to prepare theintermediate layer, Al₂O₃ may be deposited on the electroconductivesupport by anodizing process, or an organic material such aspoly-para-xylylene (parylene), or an inorganic material such as SiO₂,SnO₂, TiO₂, ITO or CeO₂ may be deposited on the electroconductivesupport by vacuum thin film forming method. It is proper that thethickness of the intermediate layer be 5 μm or less.

[0100] Examples of a resin for use as a material for the formation ofthe protective layer include ABS resin, ACS resin, copolymer of olefinand vinyl monomer, chlorinated polyether, allyl resin, phenolic resin,polyacetal polyamide, polyamideimide, polyacrylate, polyallyl sulfone,polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylicresin, polymethylpentene, polypropylene, polyphenylene oxide,polysulfone, polystyrene, AS resin, butadiene-styrene copolymer,polyurethane, polyvinyl chloride, polyvinylidene chloride and epoxyresin. The protective layer may further comprise a fluorine-containingresin such as polytetrafluoroethylene, and a sllicone resin to improvethe abrasion resistance. In addition, inorganic materials such astitanium oxide, tin oxide and potassium titanate may be dispersed in theabove mentioned fluorine-containing resin and silicone resin. Theprotective layer may be provided on the photoconductive layer by theconventional coating method. The thickness of the protective layer ispreferably in the range of about 0.1 to 10 μm. Furthermore, avacuum-deposited thin film of a-C or a-SiC may be used as the protectivelayer in the present invention.

[0101] The charge transport materials include a positive hole transportmaterial and an electron transport material.

[0102] The positive hole transport materials may be, for example,poly-N-carbazole and derivatives thereof, poly-γ-carbazolylethylglutamate and derivatives thereof, a condensation product of pyreneand formaldehyde and derivatives thereof, polyvinyl pyrene, polyvinylphenanthrene, oxazole derivatives, imidazole derivatives andtriphenylamine derivatives. Stilbene compounds of the following formula(4) may also be suitably used for reasons of excellent chargetransporting properties:

[0103] wherein r₁ and r₂ stand, independently from each other, for asubstituted or unsubstituted alkyl group or a substituted orunsubstituted aryl group, r₃ and r₄ stand, independently from eachother, for a hydrogen atom, a substituted or unsubstituted alkyl group,a substituted or unsubstituted aryl group, or a heterocyclic group, withthe proviso that r₁ and r₂ may together form a ring, and Ar₁ stands fora substituted or unsubstituted aryl group or a heterocyclic group.

[0104] Illustrative of suitable stilbene compounds are shown in Tables3-12. The present invention is not limited to these compounds. In Tables3-12, R₁, R₂, Ar₁, R₃ and R₄ represent those corresponding to the abovegeneral formula (4). TABLE 3 Compound No. R₁ R₂ Ar₁ R₃ R₄ 1 CH₃ CH₃

2 H

3 ″

4 ″

5 ″

6 ″

7 ″

8 ″

9 CH₃

10 H

[0105] TABLE 4 Compound No. R₁ R₂ Ar₁ R₃ R₄ 11

—CH₃

12

13

14

15

16

17

18

19

20

[0106] TABLE 5 Compound No. R₁ R₂ Ar₁ R₃ R₄ 21

22

23

24

25

26

27

28

29

[0107] TABLE 6 Com- pound No. R₁ R₂ Ar₁ R₃ R₄ 30

31

32

33

34

H

35

36

H

[0108] TABLE 7 Compound No. R₁ R₃ Ar₁ R₃ R₄ 37

38

39

40

[0109] TABLE 8 Compound No. R₁ R₂ Ar₁ R₃ R₄ 41

42

43

44

45

46

47

48

49

50

[0110] TABLE 9 Com- pound No. R₁ R₂ Ar₁ R₃ R₄ 51

52

53

54

55

56

57

58

59

60

[0111] TABLE 10 Compound No. R₁ R₂ Ar₁ R₃ R₄ 61

62

—CH₃ —CH₃ 63

—C₃H₅ —C₂H₅ 64

—CH₃ 65

66

67

68

69

70

[0112] TABLE 11 Com- pound No. R₁ R₂ Ar₁ R₃ R₄ 71

72 ″ ″ ″

73 ″ ″ ″

74 ″ ″ ″

75 ″ ″ ″

76 ″ ″ ″

77 ″ ″ ″

78 ″ ″ ″

79 ″ ″ ″

80 ″ ″ ″

[0113] TABLE 12 Com- pound No. R₁ R₂ Ar₁ R₃ R₄ 81

82 ″ ″ ″

83 ″ ″ ″

84 ″ ″ ″

85 ″ ″ ″

86 ″ ″ ″

87 ″ ″ ″

88 ″ ″ ″

89 ″ ″ ″

[0114] As a positive hole transport material, there may be mentioned thefollowing compounds represented by the general formulas (10) to (27).

[0115] (1) Compound Represented By the Following General Formula(10)(Described in Japanese Laid-Open Patent Applications Nos. 55-154955and 55-156954):

[0116] wherein R¹ is methyl group, ethyl group, 2-hydroxyethyl 2 groupor 2-chloroethyl group; R² is methyl group, ethyl group, benzyl group orphenyl group; R³ is a hydrogen atom, a chlorine atom, a bromine atom, analkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4carbon atoms, a dialkylamino group or nitro group.

[0117] Examples of the above compound represented by the general formula(10) are 9-ethylcarbazole-3-aldehyde-1-methyl-1-phenylhydrazone,9-ethylcarbazole-3-aldehyde-1-benzyl-1-phenylhydrazone, and9-ethylcarbazole-3-aldehyde-1,1-diphenylhydrazone.

[0118] (2) Compound Represented by the Following General Formula (11)(Described in Japanese Laid-Open Patent Application No. 55-52063):

[0119] wherein Ar is a naphthalene ring, anthracene ring, styryl ring,each of which may have a substituent, a pyridine ring, furan ring orthiophene ring; and R is an alkyl group or benzyl group.

[0120] Examples of the above compound represented by the general formula(11) are 4-diethylaminostyryl-3-aldehyde-1-methyl-1-phenylhydrazone, and4-methoxynaphthalene-1-aldehyde-1-benzyl-1-phenyihydrazone.

[0121] (3) Compound Represented by the Following General Formula (12)(Described in Japanese Laid-Open Patent Application No. 56-81850):

[0122] wherein R¹ is an alkyl group, benzyl group, phenyl group ornaphthyl group, R² is a hydrogen atom, an alkyl group having 1 to 3carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, adialkylamino group, a diaralkylamino group or a diarylamino group, n isan integer of 1 to 4, with the proviso that when n is 2 or more, R² maybe the same or different; and R³ is a hydrogen atom or methoxy group.

[0123] Examples of the above compound represented by the general formula(12) are 4-methoxybenzaldehyde-1-methyl-1-phenylhydrazone,2,4-dimethoxybenzaldehyde-1-benzyl-1-phenylhydrazone,4-diethylaminobenzaldehyde-1,1-diphenylhydrazone,4-methoxybenzaldehyde-1-benzyl-1-(4-methoxy)phenylhydrazone,4-diphenylaminobenzaldehyde-1-benzyl-1-phenylhydrazone, and4-dibenzylaminobenzaldehyde-1,1-diphenylhydrazone.

[0124] (4) Compound Represented by the Following General Formula (13)(Described in Japanese Laid-Open Patent Application No. 51-10983):

[0125] wherein R¹ is an alkyl group having 1 to 11 carbon atoms, asubstituted or unsubstituted phenyl group, or a heterocyclic group; R²and R³ are each independently a hydrogen atom, an alkyl group having 1to 4 carbon atoms, a hydroxyalkyl group, chloroalkyl group, or asubstituted or unsubstituted aralkyl group, with the proviso that R² andR³ may form a nitrogen-containing heterocyclic ring in combination; andR⁴, which may be the same or different, each is a hydrogen atom, analkyl group having 1 to 4 carbon atoms, an alkoxyl group or a halogenatom.

[0126] Examples of the above compound represented by the followinggeneral formula (13) are 1,1-bis(4-dibenzylaminophenyl)propane,tris(4-diethyl-aminophenyl)methane,1,1-bis(4-dibenzylaminophenyl)propane, and2,2′-dimethyl-4,4′bis(diethylamino)triphenyimethane.

[0127] (5) Compound Represented by the Following General Formula (14)(Described in Japanese Laid-Open Patent Application No. 51-94829):

[0128] wherein R is a hydrogen atom or a halogen atom and Ar is asubstituted or unsubstituted phenyl group, naphthyl group, anthryl groupor carbazolyl group.

[0129] Examples of the above compound represented by the followinggeneral formula (14) are 9-(4-diethylaminostyryl)anthracene and9-bromo-10-(4-diethylaminostyryl)anthracene.

[0130] (6) Compound Represented by the Following General Formula (15)(Described in Japanese Laid-Open Patent Application No. 52-128373):

[0131] wherein R¹ is a hydrogen atom, a halogen atom, a cyano group, analkoxyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to4 carbon atoms; and Ar is

[0132] where R¹ is an alkyl group having 1 to 4 carbon atoms; R³ is ahydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbonatoms, an alkoxyl group having 1 to 4 carbon atoms, or a dialkylaminogroup; n is an integer of 1 or 2 with the proviso that when n is 2, R³may be the same or different; and R⁴ and R⁵ are each a hydrogen atom, asubstituted or unsubstituted alkyl group having 1 to 4 carbon atoms, ora substituted or unsubstituted benzyl group.

[0133] Examples of the above compound represented by the general formula(15) are 9-(4-dimethylaminobenzylidene)-fluorene, and3-(9-fluorenylidene)-9-ethylcarbazole.

[0134] (7) Compound (16) (Described in Japanese Laid-Open PatentApplication No. 56-29245):

[0135] wherein R is a carbazolyl group, pyridine group, thienyl group,indolyl group, furyl group, a substituted or unsubstituted phenyl group,a substituted or unsubstituted styryl group, a substituted orunsubstituted naphthyl group, or a substituted or unsubstituted anthrylgroup, with the substituent being selected from the group consisting ofa dialkylamino group, an alkyl group, an alkoxyl group, a carboxyl groupand an ester group thereof, a halogen atom, a cyano group, anaralkylamino group, an N-alkyl-N-aralkylamino group, an amino group, anitro group and an acetylamino group.

[0136] Examples of the above compound represented by the general formula(16) are 1,2-bis(4-diethylaminostyryl)benzene, and1,2-bis(2,4-dimethoxystyryl)benzene.

[0137] (8) Compound Represented by the Following General Formula (17)(Described in Japanese Laid-Open Patent Application No. 58-58552):

[0138] wherein R¹ is a lower alkyl group, a substituted or unsubstitutedphenyl group, or benzyl group; R² and R³ are each a hydrogen atom, alower alkyl group, a lower alkoxyl group, a halogen atom, a nitro group,or an amino group which may have as a substituent a lower alkyl group orbenzyl group; and n is an integer of 1 or 2.

[0139] Examples of the above compound represented by the general formula(17) are 3-styryl-9-ethylcarbazole, and 3-(4-methoxystyryl)-9-ethylcarbazole.

[0140] (9) Compound Represented by the Following General Formula(18)(Described in Japanese Laid-Open Patent Application No. 57 73075):

[0141] wherein R¹ is a hydrogen atom, an alkyl group, an alkoxyl groupor a halogen atom; R² and R³ are each an alkyl group, a substituted orunsubstituted aralkyl group, or a substituted or unsubstituted arylgroup; R⁴ is a hydrogen atom or a substituted or unsubstituted phenylgroup; and Ar is a substituted or unsubstituted phenyl group or asubstituted or unsubstituted naphthyl group.

[0142] Examples of the above compound represented by the general formula(18) are 4-diphenylaminostilbene, 4-dibenzylaminostilbene,4-ditolylaminostilbene, 1-(4-diphenylaminostyryl)-naphthalene, and1-(4-diethylaminostyryl)naphthalene.

[0143] Compound represented by the following general formula (19)(described in Japanese Laid-Open Patent Application No. 58-198043):

[0144] wherein n is an integer of 0 or 1; R¹ is a hydrogen atom, analkyl group or a substituted or unsubstituted phenyl group; Ar¹ is asubstituted or unsubstituted aryl group; R⁵ is a substituted orunsubstituted alkyl group or a substituted or unsubstituted aryl group;and A is 9-anthryl group, a substituted or unsubstituted carbazolylgroup or a group of the formula:

[0145] where R² is a hydrogen atom, an alkyl group, an alkoxyl group, ahalogen atom or —NR³R⁴ where R³ and R⁴ are each an alkyl group, asubstituted or unsubstituted aralkyl group or a substituted orunsubstituted aryl group, with the proviso that R³ and R⁴ may be thesame or different, or may form a ring in combination, and m is aninteger of 0 to 3, provided that when m is 2 or more R may be the sameor different and when n is 0, A and R may form a ring in combination.

[0146] Examples of the above compound represented by the general formula(19) are 4′-diphenylamino-α-phenylstilbene and4′-bis(methyl-phenyl)amino-α-phenylstilbene.

[0147] (11) Compound Represented by the Following General Formula (20)(Described in Japanese Laid-Open Patent Application No. 49-105537):

[0148] wherein R¹, R² and R³ are each a hydrogen atom, a lower alkylgroup, a lower alkoxyl group, a dialkylamino group or a halogen atom;and n is an integer of 0 or 1.

[0149] Examples of the above compound represented by the general formula(20) include1-phenyl-3-(4-diethylaminostyryl)-5-(4-diethylaminophenyl)pyrazoline and1-phenyl-3-(4-dimethylaminostyryl)-5-(4-dimethylaminophenyl)pyrazoline.

[0150] (12) Compound Represented by the Following General Formula (21)(Described in Japanese Laid-Open Patent Application No. 52-139066):

[0151] wherein R¹ and R² are each a substituted or unsubstituted alkylgroup or a substituted or unsubstlituted aryl group; and A is asubstituted amino group, a substituted or unsubstituted aryl group or anallyl group.

[0152] Examples of the above compound of formula (21) are2,5-bis(4-diethylaminophenyl)-1,3,4-oxadlazole,2-N,N-diphenylamino-5-(4-diethylaminophenyl)-1,3,4-oxadiazole, and2-(4-dimethylaminophenyl)-5-(4-diethylaminophenyl)-1,3,4 oxadlazole.

[0153] (13) Compound Represented by the Following General Formula (22)(Described in Japanese Laid-Open Patent Application No. 52-139065):

[0154] wherein X is a hydrogen atom, a lower alkyl group or a halogenatom; R is a substituted or unsubstituted alkyl group or a substitutedor unsubstituted aryl group; and A is a substituted amino group or asubstituted or unsubstituted aryl group.

[0155] Examples of the above compound represented by the followinggeneral formula (22) are2-N,N-diphenylamino-5-(N-ethylcarbazole-3-yl)-1,3,4-oxadiazole and2-(4-diethylaminophenyl)-5-(N-ethylcarbazole-3-yl)-1,3,4-oxadiazole.

[0156] (14) Compound Represented by the Following General Formula (23)(Described in Japanese Laid-Open Patent Application No. 58-32372):

[0157] wherein R¹ is a lower alkyl group, a lower alkoxyl group or ahalogen atom; n is an integer of 0 to 4; and R² and R³ may be the sameor different and are each a hydrogen atom, a lower alkyl group, a loweralkoxyl group or a halogen atom.

[0158] Examples of the benzidine compound represented by the generalformula (23) areN,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine, and3,3′-dimethyl-N,N,N′,N′-tetrakis(4-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine.

[0159] (15) Compound Represented by the Following General Formula (24)(Described in Japanese Laid-Open Patent Application No. 2-178669):

[0160] wherein R¹, R³ and R⁴ are each a hydrogen atom, amino group analkoxyl group, a thioalkoxyl group, an aryloxy group, ma ethylenedioxygroup, a substituted or unsubstituted alkyl group, a halogen atom or asubstituted or unsubstituted aryl group; R² is a hydrogen atom, analkoxyl group, a substituted or unsubstituted alkyl group or a halogenatom with the proviso that R¹, R², R³ and R⁴ are not hydrogen atoms atthe same time; and k, l, m and n are each an integer of 1 to 4 with theproviso that when each is an integer of 2, 3 or 4, R¹, R², R³ and R⁴ maybe independently the same or different.

[0161] Examples of the biphenylamine compound represented by the generalformula (24) are 4′-methoxy-N,N-diphenyl-[1,1′-biphenyl]-4-amine,4′-methyl-N, N′-bis(4-methylphenyl)-[1,1′-biphenyl]-4-amine, and4′-methoxy-N,N′-bis(4-methylphenyl-[1,1′-biphenyl]-4-amine.

[0162] (16) Compound (25) (Described in Japanese Laid-Open PatentApplication No. 3-285960):

[0163] wherein Ar is a condensed polycyclic hydrocarbon group having 18or less carbon atoms; and R¹ and R² may be the same or different and areeach a hydrogen atom, a halogen atom, a substituted or unsubstitutedalkyl group, an alkoxyl group or a substituted or unsubstituted phenylgroup.

[0164] Examples of the triarylamine compound represented by the generalformula (25) are 1-diphenylaminopyrene and 1-di(p-tolylamino)pyrene.

[0165] (17) Compound Represented by the Following General Formula (26)(Described in Japanese Laid-Open Patent Application No. 62-98394):

A—CH═CH—Ar—CH═CH—A  (26)

[0166] wherein Ar is a substituted or unsubstituted aromatic hydrocarbongroup; and A is

[0167] where Ar′ is a substituted or unsubstituted aromatic hydrocarbongroup; and R¹ and R² are each a substituted or unsubstituted alkyl groupor a substituted or unsubstituted aryl group.

[0168] Examples of the diolefinic aromatic compound represented by thegeneral formula (26) are 1,4-bis(4-diphenylaminostyryl)benzene and1,4-bis[4-di(p-tolyl) aminostyryl]benzene.

[0169] (18) Compound Represented by the Following General Formula (27)(Described in Japanese Laid-Open Patent Application No. 4-230764):

[0170] wherein Ar is an aromatic hydrocarbon group; R is a hydrogenatom, a substituted or unsubstituted alkyl group or a substituted orunsubstituted aryl group; and n is an integer of 0 or 1 and m is aninteger of 1 or 2, provided that when n=0 and m=1, Ar and R may form aring in combination.

[0171] Examples of the styrylpyrene compound represented by formula (27)are 1-(4-diphenylaminostyryl)pyrene, and1-[4-di(p-tolyl)aminostyryl]pyrene.

[0172] Electron transport materials may be, for example, chloroanil,bromoanil, tetracyanoethylene, tetracyanoquinodimethane,2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone,2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone,2,6,8-trinitroindeno-4H-indeno[1,2-b]thiophen-4-one and1,3,7-trinitrodibenzothiophene-5,5-dioxide.

[0173] In particular, 2,3-diphenylindene compound of the followingformula (5).

[0174] wherein R₁-R₄ stand, independently from each other, for ahydrogen atom, a halogen atom, a substituted or unsubstituted alkylgroup, a cyano group or a nitro group, and A and B stand, independentlyfrom each other, for a hydrogen atom, a halogen atom, a substituted orunsubstituted aryl group, a cyano group, an alkoxycarbonyl group or anaryloxycarbonyl group, is preferably employed because of its excellentelectron transporting performance. Of the compounds of the formula (4),2,3-diphenyl-1-indenylidene)marononitrile of the following formula (28)may be particularly suitably used:

[0175] Further, the compounds of the following formulas (29) and (30)may also be preferably used as the electron transport material forreasons of excellent electron transporting performance:

[0176] The above-mentioned charge transport materials may be used aloneor in combination of two or more.

[0177] The electrophotographic photoconductor of the present inventionmay be used for an electrophotographic machine comprising chargingmeans, exposing means, developing means, transfer means, cleaning means,charge removing means and an electrophotographic photoconductor and fora process cartridge for an electrophotographic machine comprisingcharging means and an electrophotographic photoconductor.

[0178] Further, the reaction product of the present invention is usefulas the photoconductive material for use in the electrophotographicphotoconductor, and in addition, as an electronic device for utilizationin the field of electronics such as solar batteries and optical disks.

[0179] The present invention will be described with reference toexamples but is not limited thereby. Parts are by weight.

EXAMPLE 1

[0180] (Preparation of Reaction Product No. 1-A)

[0181] 0.1 Mol of 1,4-bisbenzyl, 0.2 mol of diaminomaleonitrile andacetaic acid were stirred under reflux for 6 hours. The mixture was thenallowed to be cooled to room temperature, thereby precipitatingcrystals. The crystals were collected by filtration and isolated bycolumn chromatography using chloroform as a developing solvent to obtaina crude product. This was recrystallized from toluene to obtain anitrile compound represented by the formula (6) shown below with a yieldof 80%. The nitrile compound (6) has a melting point of 270-274° C. Aninfrared absorption spectrum of the nitrile compound (6) is shown inFIG. 33. The elementary analysis of the nitrile compound (6) gave asfollows: C H N Calculated 74.32 2.74 23.21 Found 74.06 2.90 23.03 (6)

[0182] 0.2 Mole of the nitrile derivative A of the formula (6), 0.2 molof phthalonitrile, 0.1 mol of cuprous chloride and 200 ml ofα-chloronaphthalene were mixed with stirring. The mixture was thengradually heated and maintained at 170-180° C. with stirring under anitrogen gas stream for 5 hours. After completion of the reaction, thereaction mixture was allowed to be cooled to 130° C. and immediatelyfiltered. The solid phase was then washed well with α-chloronaphthaleneand then several times with methanol, toluene and water and dried toobtain a reaction product (Exemplified Compound No. 1-A) with a yield of76%

EXAMPLE 2

[0183] (Preparation of Reaction Product No. 1-B)

[0184] 0.5 Mole of the nitrile compound (A) represented by the formula(6) obtained in Example 1, 0.3 mol of phthalonitrile, 0.11 mol ofTi(OBu)₄ and 200 ml of octanol were mixed with stirring. The mixture wasgradually heated to 160° C. and maintained at 150-160° C. with stirringunder a nitrogen gas stream for 6 hours. After completion of thereaction, the reaction mixture was allowed to be cooled and filtered.The solid phase was then washed well with octanol and then several timeswith methanol, toluene and water and dried to obtain a reaction product(Compound No. 1-B) with a yield of 75%.

[0185] The thus obtained Compound No. 1-B was analyzed by massspectrometer under the following conditions:

[0186] LC/MS Device:

[0187] Maker: JEOL

[0188] Name of Device: Mass Analyzer

[0189] Number of Device: MS700

[0190] Conditions of Measurement:

[0191] Ionization: ESI method; +ion detection

[0192] Sample flow rate: 25 μL/min

[0193] Sample injection mode: infusion

[0194] Ring voltage: 80V

[0195] Skimmer voltage: 0V

[0196] Preparation of Sample: Sample was dissolved in formic acid andthe solution was diluted with 50% aqueous formic acid to a concentrationof 50 ppm

[0197] The results of the mass spectrometry of Compound No. 1-B areshown in FIG. 26. Peaks corresponding to molecular weight of thecompound represented by the above formula (8) (molecular weight: 1383)and the compound represented by the above formula (9) (molecular weight:576) were observed, suggesting the presence of these compounds.

[0198]FIG. 27 is an infrared absorption spectrum of the reactionproduct. The fluorescent X-ray spectroscopy revealed the presence of Tiin the reaction product.

[0199] For the purpose of investigating reproducibility of the reactionproduct provided by the present invention, manufacture of the reactionproduct was repeated 10 times in the same manner as described in Example2. It was found that the products obtained showed the same MS and IRspectra as shown in FIGS. 26 and 27, indicating that the reactionproduct of the present invention was able to be produced with highreproducibility.

EXAMPLE 3

[0200] 0.0016 Mole of the nitrile compound A described in Example 1,0.32 mol of phthalonitrile, 0.09 mol of Ti(OBu)₄, 0.16 mole of urea and200 ml of octanol were mixed with stirring. The mixture was graduallyheated to 150° C. and maintained at 150-160° C. with stirring under anitrogen gas stream for 6 hours. After completion of the reaction, thereaction mixture was allowed to be cooled and filtered. The solid phasewas then washed well with octanol and then several times with methanol,toluene and water and dried to obtain a reaction product (Compound No.1-C) with a yield of 75%.

[0201] This product (20 g) was then subjected to an acid treatment usingan acid pasting method. Thus, the product was dissolved little by littlewith stirring in 200 g of concentrated sulfuric acid while being cooledin an ice bath. The mixture was then reacted for 1 hour and subsequentlypoured into 2000 ml of ice water to form crystals. The crystals wereseparated by filtration and washed with distilled water until no acidwas detected in the washed water. After drying, 18 g of a reactionproduct was obtained.

EXAMPLE 4

[0202] A nitrile derivative (B) represented by the formula (31) wasprepared according to the following reaction scheme (DAMN meansdiaminomaleonitrile):

[0203] In a reactor, 0.15 mol of SeO₂, 120 ml of dioxane and 5 ml ofwater were charged and heated at 50° C. for 1 hour with stirring, towhich a solution of 0.05 ml of (a) dissolved in 20 ml of dioxane wasadded dropwise. The mixture was then reacted for 8 hours under reflux.Thereafter, the reaction mixture, while hot, was filtered to removesolids. The solvent in the filtrate was removed by distillation to leavethe above compound (b).

[0204] The compound (b) was mixed with 0.1 mol of diaminomaleonitrile,0.01 mol of p-toluenesulfonic acid and 200 ml of dioxane. The mixturewas refluxed for 2 hours and then allowed to be cooled to roomtemperature, followed by removal of the solvent by distillation. Theresidue was mixed with 200 ml of methanol to precipitate crystals. Thecrystals were collected by filtration, washed several times withmethanol and dried. The crystals were then isolated by columnchromatography using dichloromethane as a developing solvent to obtain acrude product. This was recrystallized from dioxane to the obtainnitrile derivative (B) of the formula (31) with a yield of 60%. Aninfrared absorption spectrum of the nitrile derivative (B) is shown inFIG. 34. The results of the elementary analysis are shown in Table 14.TABLE 14 C H N Calculated 64.67 1.81 33.52 Found 64.50 1.92 33.34 (31)

[0205] 0.0016 Mole of the nitrile compound (31), 0.32 mol ofphthalonitrile, 0.09 mol of Ti(OBu)₄, 0.16 mole of urea and 200 ml ofoctanol were mixed with stirring. The mixture was gradually heated to150° C. and maintained at 150-160° C. with stirring under a nitrogen gasstream for 6 hours. After completion of the reaction, the reactionmixture was allowed to be cooled and filtered. The solid phase was thenwashed well with octanol and then several times with methanol, tolueneand water and dried to obtain a reaction product with a yield of 70%.

[0206] This product (20 g) was then subjected to an acid treatment usingan acid pasting method. Thus, the product was dissolved little by littlewith stirring in 200 g of concentrated sulfuric acid while being cooledin an ice bath. The mixture was then reacted for 1 hour and subsequentlypoured into 2000 ml of ice water to form crystals. The crystals wereseparated by filtration and washed with distilled water until no acidwas detected in the washed water. After drying, 18 g of a reactionproduct was obtained. An infrared absorption spectrum of the reactionproduct is shown in FIG. 29.

EXAMPLE 5

[0207] A nitrile derivative (C) of the formula (32) was preparedaccording to the following reaction scheme (DAMN meansdiaminomaleonitrile):

[0208] In a reactor, 0.12 mol of SeO₂, 120 ml of dioxane and 4 ml ofwater were charged and heated at 50° C. for 1 hour with stirring, towhich a solution of 0.05 ml of the compound (c) dissolved in 20 ml ofdioxane was added dropwise. The mixture was then reacted for 8 hoursunder reflux. Thereafter, the reaction mixture, while hot, was filteredto remove solids. The solvent in the filtrate was removed bydistillation to leave the compound (d).

[0209] The compound (d) was mixed with 0.1 mol of diaminomaleonitrile,0.01 mol of p-toluenesulfonic acid and 200 ml of dioxane. The mixturewas refluxed for 2 hours and then allowed to be cooled to roomtemperature, followed by removal of the solvent by distillation. Theresidue was mixed with 200 ml of methanol to precipitate crystals. Thecrystals were collected by filtration, washed several times withmethanol and dried. The crystals were then isolated by columnchromatography using dichloromethane as a developing solvent to obtain acrude product. This was recrystallized from dioxane to obtain thenitrile derivative (C) of the formula (32) with a yield of 55%. Thenitrile derivative was found to have a melting point of 279-284° C. Aninfrared absorption spectrum of the nitrile derivative (C) is shown inFIG. 35. The results of the elementary analysis are shown in Table 15.TABLE 15 C H N Calculated 64.67 1.81 33.52 Found 64.55 1.87 33.40 (32)

[0210] 0.0016 Mole of the nitrile derivative (C) of the formula (32),0.32 mol of phthalonitrile, 0.09 mol of Ti(OBu)₄, 0.16 mole of urea and200 ml of octanol were mixed with stirring. The mixture was graduallyheated to 150° C. and maintained at 150-160° C. with stirring under anitrogen gas stream for 6 hours. After completion of the reaction, thereaction mixture was allowed to be cooled and filtered. The solid phasewas then washed well with octanol and then several times with methanol,toluene and water and dried to obtain a reaction product with a yield of71%.

[0211] This product (20 g) was then subjected to an acid treatment usingan acid pasting method. Thus, the product was dissolved little by littlewith stirring in 200 g of concentrated sulfuric acid while being cooledin an ice bath. The mixture was then reacted for 1 hour and subsequentlypoured into 2000 ml of ice water to form crystals. The crystals wereseparated by filtration and washed with distilled water until no acidwas detected in the washed water. After drying, 18 g of a reactionproduct was obtained. An infrared absorption spectrum of the reactionproduct is shown in FIG. 30.

EXAMPLE 6

[0212] [Crystal Treatment 1 of Compound No. 1-C]

[0213] The reaction product (1 g) obtained in Example 3 (reactionproduct after the acid pasting treatment (the same shall applyhereinafter)) was placed in an Erlenmeyer flask together with 20 ml ofN,N-dimethylformamide and heated under reflux conditions for 4 hours.The mixture was cooled to room temperature and filtered to collectsolids. The solids were dried to obtain 0.96 g of a reaction product.

EXAMPLE 7

[0214] [Crystal Treatment 2 of Compound No. 1-C]

[0215] The reaction product (1 g) obtained in Example 3 was placed in anErlenmeyer flask together with 20 ml of methyl ethyl ketone and heatedunder reflux conditions for 4 hours. The mixture was cooled to roomtemperature and filtered to collect solids. The solids were dried toobtain 0.97 g of a reaction product.

EXAMPLE 8

[0216] [Crystal Treatment 3 of Compound No. 1-C]

[0217] The reaction product (1 g) obtained in Example 3 was placed in anErlenmeyer flask together with 20 ml of o-chlorobenzene and heated underreflux conditions for 4 hours. The mixture was cooled to roomtemperature and filtered to collect solids. The solids were dried toobtain 0.97 g of a reaction product.

EXAMPLE 9

[0218] [Crystal Treatment 4 of Compound No. 1-C]

[0219] The reaction product (1 g) obtained in Example 3 was placed in anErlenmeyer flask together with 20 ml of cyclohexanone and heated underreflux conditions for 4 hours. The mixture was cooled to roomtemperature and filtered to collect solids. The solids were dried toobtain 0.98 g of a reaction product.

EXAMPLE 10

[0220] 0.0016 Mole of the nitrile derivative (B) of the formula (31)obtained in Example 4, 0.32 mol of phthalonitrile, 0.09 mol of Ti(OBu)₄,0.16 mole of urea and 200 ml of octanol was gradually heated to 150° C.and maintained at 150-160° C. with stirring under a nitrogen gas streamfor 6 hours. After completion of the reaction, the reaction mixture wasallowed to be cooled and filtered. The solid phase was then washed wellwith octanol and then several times with methanol, toluene and water anddried to obtain a reaction product with a yield of 70%.

[0221] This product (5 g) was dissolved little by little with stirringin 50 g of concentrated sulfuric acid while being cooled in an ice bath.The mixture was then reacted for 1 hour and subsequently poured into 500ml of ice water to form crystals. The crystals were separated byfiltration and washed with distilled water until no acid was detected inthe washed water, thereby obtaining 20 g of a wet cake (solid mattercontent: 20%).

EXAMPLE 15

[0222] The wet cake (15 g) of the reaction product obtained in Example10 was mixed with 12 g of distilled water and 120 g of tetrahydrofuranwith stirring for 6 hours. The mixture was then filtered and the solidphase was dried to obtain 3.5 g of a reaction product.

EXAMPLE 12

[0223] The wet cake (15 g) of the reaction product obtained in Example10 was mixed with 12 g of distilled water and 120 g of toluene at roomtemperature with stirring for 6 hours. The mixture was then filtered andthe solid phase was dried to obtain 3.6 g of a reaction product.

EXAMPLE 13

[0224] The wet cake (15 g) of the reaction product obtained in Example10 was mixed with 12 g of distilled water and 120 g of 1,4-dioxane atroom temperature with stirring for 6 hours. The mixture was thenfiltered and the solid phase was dried to obtain 3.6 g of a reactionproduct.

EXAMPLE 14

[0225] The wet cake (15 g) of the reaction product obtained in Example10 was mixed with 12 g of distilled water and 120 g ofN,N-dimethylformamide at 80° C. with stirring for 6 hours. The mixturewas then filtered and the solid phase was dried to obtain 3.6 g of areaction product.

EXAMPLE 15

[0226] [Preparation of Product 1-B]

[0227] 1.95 Grams (4.0 mols) of the intermediate product nitrilederivative (A) of the formula (6) obtained in Example 1, 105.64 g (0.808mol) of phthalonitrile, 74.87 g (0.22 mols) of Ti(OBu)₄, 24.26 g (0.400mol) and 100 ml of 1-octanol were placed in a reactor and graduallyheated to 155° C. and maintained at 150-155° C. with stirring under anitrogen gas stream for 5 hours. After completion of the reaction, thereaction mixture was allowed to be cooled to 70° C. and mixed with 400ml of methanol. The mixture was again heated at 70° C. with stirring for45 minutes. After being allowed to stand overnight, the solid phase wasthen filtered, washed thrice with toluene, twice with methanol and oncewith water and dried to obtain a reaction product.

EXAMPLE 16

[0228] The reaction product (40.0 g) obtained in Example 15 was addedlittle by little to 640 g of concentrated sulfuric acid through 30minutes while maintaining the temperature at 4-9° C. The mixture wasthen heated at 6-9° C. for 1 hour with stirring and then added dropwisein 4 liters of ice water through 30 minutes. After stirring for 30minutes, solids were separated by filtration. The separated solid phasewas mixed with 4 liters of ion-exchanged water with stirring and againfiltered. Such washing and filtration procedures were repeated 4 timesmore to obtain 297.7 g of a wet cake (solid matter content: 12.7%,yield: 94.5%)

EXAMPLE 17

[0229] The wet cake (153.86 g) obtained in Example 16 was dried in avacuum dryer at 70° C. for 2 days to obtain 19.52 g of a reactionproduct.

EXAMPLE 18

[0230] The reaction product obtained in Example 15 was subjected to anacid-paste treatment using concentrated sulfuric acid in the same manneras described in Example 16 to obtain a wet cake. The wet cake (8.00 g,solid matter content: 13.1%) was mixed with 2.5 g of ion-exchanged waterand 42.0 g of 1-methyl-2-pyrrolidinone with stirring at room temperaturefor 6 hours. This was then mixed with methanol and the solid phase wasseparated by filtration to give 1.03 g of a reaction product (yield:98.1%)

EXAMPLE 19

[0231] The wet cake (8.00 g) obtained in Example 16 was mixed with 2.5 gof ion-exchanged water and 42.0 g of 1-methyl-2-pyrrolidinone withstirring at room temperature for 2 hours. This was then mixed withmethanol and the solid phase was separated by filtration to give 1.01 gof a reaction product (yield: 99.6%).

EXAMPLE 20

[0232] Example 19 was repeated in the same manner as described exceptthat the stirring time was increased to 48 hours. 1.01 Grams of areaction product was obtained (yield: 99.6%)

EXAMPLE 21

[0233] Example 18 was repeated in the same manner as described exceptthat 1,3-dimethyl-2-imidazoline was substituted for1-methyl-2-pyrrolidinone. 1.04 Grams of a reaction product was obtained(yield: 99.0%)

EXAMPLE 22

[0234] Example 18 was repeated in the same manner as described exceptthat the stirring time was increased to 30 hours. 1.01 Grams of areaction product was obtained (yield: 99.6%).

Example 23

[0235] Example 18 was repeated in the same manner as described exceptthat the treatment temperature was raised to 80° C. 1.01 Grams of areaction product was obtained (yield: 99.6%).

EXAMPLE 24

[0236] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of the reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 5 minutes to a mixed solvent composed of 100 mlof dichloromethane and 100 ml of methanol in an ice bath with stirringto form crystals. The crystals were separated by filtration and washedwith distilled water until no acid was detected in the washed water anddried, thereby obtaining a reaction product.

EXAMPLE 25

[0237] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of the reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 75 minutes to a mixed solvent composed of 100 mlof dichloromethane and 100 ml of methanol in an ice bath with stirringto form crystals. The crystals were separated by filtration and washedwith distilled water until no acid was detected in the washed water anddried, thereby obtaining a reaction product.

Example 26

[0238] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of The reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 5 minutes to 200 ml of ice water to formcrystals. The crystals were separated by filtration and washed withdistilled water until no acid was detected in the washed water anddried, thereby obtaining a reaction product.

Example 27

[0239] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of The reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 5 minutes to 50 ml of N,N-dimethylformamide in anice bath with stirring. Thereafter, 50 ml of methanol was added to themixture and stirred for 1 hour to form crystals. The crystals wereseparated by filtration and washed with distilled water until no acidwas detected in the washed water and dried, thereby obtaining a reactionproduct.

EXAMPLE 28

[0240] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of The reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 5 minutes to 50 ml of cylohexane in an ice bathwith stirring. Thereafter, 50 ml of methanol was added to the mixtureand stirred for 1 hour to form crystals. The crystals were separated byfiltration and washed with distilled water until no acid was detected inthe washed water and dried, thereby obtaining a reaction product.

EXAMPLE 29

[0241] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of The reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 5 minutes to 50 ml of isopropyl ether in an icebath with stirring. Thereafter, 50 ml of methanol was added to themixture and stirred for 1 hour to form crystals. The crystals wereseparated by filtration and washed with distilled water until no acidwas detected in the washed water and dried, thereby obtaining a reactionproduct.

Example 30

[0242] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of The reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 5 minutes to 50 ml of methyl ethyl ketone in anice bath with stirring. Thereafter, 50 ml of methanol was added to themixture and stirred for 1 hour to form crystals. The crystals wereseparated by filtration and washed with distilled water until no acidwas detected in the washed water and dried, thereby obtaining a reactionproduct.

EXAMPLE 31

[0243] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of the reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 5 minutes to 50 ml of methanol with stirring inan ice bath to form crystals. The crystals were separated by filtrationand washed with distilled water until no acid was detected in the washedwater and dried, thereby obtaining a reaction product.

Example 32

[0244] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of The reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 5 minutes to 50 ml of tetrahydrofuran in an icebath with stirring. Thereafter, 50 ml of methanol was added to themixture and stirred for 1 hour to form crystals. The crystals wereseparated by filtration and washed with distilled water until no acidwas detected in the washed water and dried, thereby obtaining a reactionproduct.

EXAMPLE 33

[0245] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of The reaction product obtained in Example 3was added through 1 minute. The mixture was then stirred for 45 minutesat room temperature to dissolve the Product and then allowed to sand for25 minutes. After removal of the supernatant, the mixture was mixed with50 ml of methanol to form crystals. The crystals were separated byfiltration, placed in a beaker, washed with hot water, and thenfiltered. Such washing with hot water and filtration procedures wererepeated two times more. Thereafter, the crystals were dispersed in 50ml of fluorobenzene, stirred for 15 minutes at room temperature,separated by filtration and dried to obtain a reaction product.

Example 34

[0246] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of The reaction product obtained in Example 3was dissolved. The mixture was then stirred for 1 hour and subsequentlyadded dropwise through 20 seconds to a mixed solvent consisting of 100ml of dichloromethane and 100 ml methanol with stirring in an ice bathto form crystals. The crystals were separated by filtration and washedwith distilled water until no acid was detected in the washed water anddried, thereby obtaining a reaction product.

[0247] Each of the products or treated products obtained in Examples6-14, 18-22 and 24-34 was measured for X-ray diffraction spectrumthereof to give the results shown in FIGS. 1-24 and 25, respectively.The X-ray diffraction spectra were measured under conditions shownbelow. Wet cake samples were measured after having been dried. X-raytube: Cu (wavlength: 1.54 Å) Voltage: 50 kV Current: 30 mA Scanningspeed: 2 deg/min. Scanning scope: 3-40 deg

[0248] The X-ray diffraction spectrum shown in FIG. 5 has no diffractionpeaks having a half-value width of 1° or less, indicating that theproduct is amorphous. The X-ray diffraction spectra of FIGS. 1-4 and6-24 have peaks with a half-value width of 1° or less, indicating thatthe products are crystalline in nature. Further, differences in theX-ray patterns suggest that the crystal structures of the products aredifferent from each other.

EXAMPLE 35

[0249] Example 2 was repeated in the same manner as described exceptthat 1,3-diiminoindoline (R₂—R₅═H in the general formula (3)) wassubstituted for the phthalonitrile. In this case, a crystalline reactionproduct similar to the product of Example 2 was obtained. Using thisproduct, Example 24 was repeated in the same manner as described. It wasconfirmed that the resulting product had charge generating properties.

APPLICATION EXAMPLE 1

[0250] A dispersion containing 3 parts of the product obtained inExample 24, 1 part of polyvinyl butyral resin (BM-S manufactured bySekisui Chemical Co., Ltd.) and 80 parts of methyl ethyl ketone wasplaced in a ball mill pot and milled for 3 hours using PSZ balls with adiameter of 2 mm to obtain a coating liquid for forming a chargegeneration layer. This was applied on an aluminum plate and dried at100° C. for 20 minutes to form a charge generation layer having athickness of about 0.3 μm. A coating liquid for forming a chargetransport layer was prepared by mixing 7 parts by weight of a positivehole charge transporting material of the formula (33) shown below, 10parts by weight of a commercially available polycarbonate resin (PCX-5manufactured by Teijin Chemicals Ltd.), 68 parts by weight ofdichloromethane and 0.0002 part by weight of a commercially availablesilicone oil (KF50 manufactured by Shin-Etsu Chemical Co., Ltd.). Thecoating liquid was applied on the above-prepared charge generation layerand dried at 110° C. for 20 minutes to obtain a charge transport layerhaving a thickness of about 28 μm, thereby obtaining anelectrophotographic photoconductor.

APPLICATION EXAMPLE 2

[0251] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 25 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 2.

APPLICATION EXAMPLE 3

[0252] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 26 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 3.

APPLICATION EXAMPLE 4

[0253] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 27 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 4.

APPLICATION EXAMPLE 5

[0254] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 28 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 5.

APPLICATION EXAMPLE 6

[0255] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 29 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 6.

APPLICATION EXAMPLE 7

[0256] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 30 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 7.

APPLICATION EXAMPLE 8

[0257] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 31 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 8.

APPLICATION EXAMPLE 9

[0258] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 32 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 9.

APPLICATION EXAMPLE 10

[0259] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 33 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 10.

APPLICATION EXAMPLE 11

[0260] Application Example 1 was repeated in the same manner asdescribed except that a positive hole charge transporting materialrepresented by the formula (34) below was substituted for the chargetransporting material (33), thereby obtaining an electrophotographicphotoconductor of Application Example 11.

APPLICATION EXAMPLE 12

[0261] Application Example 1 was repeated in the same manner asdescribed except that a positive hole charge transporting materialrepresented by the formula (35) below was substituted for the chargetransporting material (33), thereby obtaining an electrophotographicphotoconductor of Application Example 12.

APPLICATION EXAMPLE 13

[0262] Application Example 1 was repeated in the same manner asdescribed except that a positive hole charge transporting materialrepresented by the formula (36) below was substituted for the chargetransporting material (33), thereby obtaining an electrophotographicphotoconductor of Application Example 13.

APPLICATION EXAMPLE 14

[0263] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 6 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 14.

APPLICATION EXAMPLE 15

[0264] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 7 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 15.

APPLICATION EXAMPLE 16

[0265] Application Example 1 was repeated in the same manner asdescribed except that the product obtained in Example 12 was substitutedfor the product of Example 24, thereby obtaining an electrophotographicphotoconductor of Application Example 16.

COMPARATIVE EXAMPLE

[0266] 0.1 Mole of phthalocyanine, 0.025 mol of Ti(OBu)₄, 0.05 mol ofurea and 200 ml of octanol were mixed with stirring. The mixture wasgradually heated to 150° C. and maintained at 150-160° C. with stirringunder a nitrogen gas stream for 6 hours. After completion of thereaction, the reaction mixture was allowed to be cooled and filtered.The solid phase was then washed well with octanol and then several timeswith methanol, toluene and water and dried to obtaintitanylphthalocyanine with a yield of 70%.

[0267] In a mixed solvent containing 2 ml of trifluoroacetic acid and 8ml of dichloromethane, 1 g of the thus obtained titanylphthalocyaninewas added through 1 minute. The mixture was then stirred for 45 minutesat room temperature to dissolve the titanylphthalocyaine and thenallowed to sand for 25 minutes. After removal of the supernatant, themixture was mixed with 50 ml of methanol to form crystals. The crystalswere separated by filtration, placed in a beaker, washed with 200 ml ofhot water, and then filtered. Such washing with hot water and filtrationprocedures were repeated two times more. Thereafter, the crystals weredispersed in 50 ml of fluorobenzene, stirred for 15 minutes at roomtemperature, separated by filtration and dried to obtain treatedtitanylphthalocyanine whose X-ray diffraction spectrum measured in thesame conditions as those giving FIGS. 1-24 is shown in FIG. 25.

[0268] Application Example 1 was repeated in the same manner asdescribed except that the above treated titanylphthalocyanine wassubstituted for the product of Example 24, thereby obtaining anelectrophotographic photoconductor of Comparative Example.

[0269] The photoconductors obtained in Application Examples 1-16 andComparative Example were measured for their electrostaticcharacteristics under conditions of 25° C./55% RH using EPA-8100manufactured by Kawaguchi Electro Works Co., Ltd. in accordance with adynamic mode. Thus, each photoconductor was negatively charged at −6 kVfor 20 seconds. Then the photoconductor was allowed to stand in the darkfor 20 seconds and the surface potential V₀ [V] was measured. Thephotoconductor was then irradiated with a monochromatic light with awavelength of 780 nm such that the illuminance on the surface of thephotoconductor was 1 μW/cm². The exposure Em½[μJ/cm² ] required toreduce the surface potential from −800V to −400 V was measured for theevaluation of sensitivity of the photoconductor to light emitted from LD(near infrared region) The results are summarized in Table 16 below.TABLE 16 V₀ [−V] Em_(1/2) [μJ/cm²] Application Example 1 870 0.35Application Example 2 1050 0.2 Application Example 3 950 0.4 ApplicationExample 4 850 0.2 Application Example 5 700 0.95 Application Example 6720 0.3 Application Example 7 680 0.5 Application Example 8 900 0.7Application Example 9 1100 0.4 Application Example 10 1160 0.4Application Example 11 600 0.8 Application Example 12 650 1.6Application Example 13 800 1.2 Application Example 14 900 0.5Application Example 15 950 0.6 Application Example 16 850 0.4Comparative Example 820 0.38

[0270] The photoconductors obtained in Application Example 1 andComparative Example were each measured for the electrostatic fatiguecharacteristics thereof using EPA-8100 manufactured by Kawaguchi ElectroWorks Co., Ltd. in accordance with a dynamic mode (rotational speed:1000 rpm). Thus, each photoconductor was repeatedly subjected tonegative charging at −6 kV and irradiation with white light for 60minutes while maintaining the current and potential at 5.6 μA and −800V,respectively. The photoconductor obtained in Example 20 was alsosubjected to the electrostatic fatigue characteristics. The change ofthe surface potential V₀ [V] is shown in Table 17.

[0271] From FIG. 17, it is seen that the photoconductor of ApplicationExample 1 is more stable in repeated electrostatic fatiguecharacteristics than photoconductor of Comparative Example. The use ofthe reaction product according to the present invention is effective forthe stability in repeated electrostatic fatigue characteristics. TABLE17 V₀ [−V] Application Example 1 820 Comparative Example 450

APPLICATION EXAMPLE 17

[0272] A charge generation layer was formed on an aluminum-deposited PETbase in the same manner as that of Application Example 1. A coatingliquid, which was a solution obtained by dissolving 8 parts by weight ofan electron transporting material of the formula (28) shown below, 11parts by weight of a polycarbonate resin (Polycarbonate Z manufacturedby Teijin Chemicals, Ltd.) and 0.02 part by weight of a silicone oil(KF50 manufactured by Shin-Etsu Chemical Co., Ltd.) in 91 parts byweight of tetrahydrofuran, was then applied to the above chargegeneration layer with a doctor blade and dried to form thereon a chargetransport layer having a thickness of 20 μm, thereby obtaining anelectrophotographic photoconductor of Application Example 17.

APPLICATION EXAMPLE 18

[0273] Application Example 17 was repeated in the same manner asdescribed except that an electron transporting material of the formula(29) shown below was used in lieu of the charge transporting material ofApplication Example 17, thereby obtaining a photoconductor ofApplication Example 18.

[0274] The photoconductors obtained in Application Examples 17 and 18were each measured for its photoconductive characteristics in the samemanner as that in Application Example 1 except that the impressionvoltage was changed to +6KV. The results are shown in Table 18. TABLE 18V₀ [+V] Em_(1/2) [μJ/cm²] Application Example 17 1100 2.50 ApplicationExample 18 1200 2.35

APPLICATION EXAMPLE 19

[0275] The reaction product obtained in Example 24 (0.5 g) was milledwith a ball mill together with 9 g of tetrahydrofuran and 10 g ofPolycarbonate Z (manufactured by Teijin Chemicals, Ltd.; a 10% by weightsolution in tetrahydrofuran), to which 10% by weight solution ofPolycarbonate Z was blended and sufficiently stirred to obtain a coatingliquid containing 2% by weight of the reaction product, 50% by weight ofPC-Z and 28% by weight of the charge transporting material of theformula (33). The coating liquid was then applied onto a Al-depositedpolyester film with a doctor blade and dried to form a single layerphotoconductive layer having a thickness of 15 μm, thereby obtaining asingle layer-type photoconductor of Application Example 19. Thephotoconductor of Application Example 19 was measured for itsphotoconductive characteristics in the same manner as that inApplication Example 1. The results are shown in Table 19. TABLE 19 V₀[−V] Em_(1/2) [μJ/cm²] Application Example 19 1150 0.6

APPLICATION EXAMPLE 20

[0276]FIG. 32 is a solution spectrum of the reaction product obtained inExample 24 (solvent: N,N-dimethylformamide). λmax was 684 nm.

[0277] A dispersion containing 3 parts of the product obtained inExample 24, 1 part of a polyvinyl butyral resin (BM-S manufactured bySekisui Chemical Co., Ltd.) and 80 parts of methyl ethyl ketone wasplaced in a ball mill pot and milled for 3 hours using PSZ balls with adiameter of 2 mm to obtain a coating liquid for forming a chargegeneration layer. This was applied to a polyethylene terephthalate sheetwith a thickness of 100 □m and then dried at 100° C. for 20 minutes toobtain a sample for measuring a light absorption spectrum. The lightabsorption spectrum is shown in FIG. 31. There is an absorption in thewavelength of 500-700 nm.

APPLICATION EXAMPLE 21

[0278] The electrophotographic photoconductor fabricated in ApplicationExample 1 was mounted on an electrophotographic device. It was foundthat the device produced clear images.

[0279] [Effect of the Invention]

[0280] The reaction product according to the present invention hascharge generating properties and good chargeability and sensitivity andcan provide excellent electrophotographic photoconductor. Theelectrophotographic photoconductor according to the present inventionpermits the application thereof for an electrophotographic device.

BRIEF DESCRIPTION OF THE DRAWINGS

[0281]FIG. 1 is an X-ray diffraction spectrum of a reaction productobtained in Example 6;

[0282]FIG. 2 is an X-ray diffraction spectrum of a reaction productobtained in Example 7;

[0283]FIG. 3 is an X-ray diffraction spectrum of a reaction productobtained in Example 8;

[0284]FIG. 4 is an X-ray diffraction spectrum of a reaction productobtained in Example 9;

[0285]FIG. 5 is an X-ray diffraction spectrum of a reaction productobtained in Example 10;

[0286]FIG. 6 is an X-ray diffraction spectrum of a reaction productobtained in Example 11;

[0287]FIG. 7 is an X-ray diffraction spectrum of a reaction productobtained in Example 12;

[0288]FIG. 8 is an X-ray diffraction spectrum of a reaction productobtained in Example 13;

[0289]FIG. 9 is an X-ray diffraction spectrum of a reaction productobtained in Example 14;

[0290]FIG. 10 is an X-ray diffraction spectrum of a reaction productobtained in Example 18;

[0291]FIG. 11 is an X-ray diffraction spectrum of a reaction productobtained in Example 19;

[0292]FIG. 12 is an X-ray diffraction spectrum of a reaction productobtained in Example 20;

[0293]FIG. 13 is an X-ray diffraction spectrum of a reaction productobtained in Example 21;

[0294]FIG. 14 is an X-ray diffraction spectrum of a reaction productobtained in Example 22;

[0295]FIG. 15 is an X-ray diffraction spectrum of a reaction productobtained in Example 24;

[0296]FIG. 16 is an X-ray diffraction spectrum of a reaction productobtained in Example 25;

[0297]FIG. 17 is an X-ray diffraction spectrum of a reaction productobtained in Example 26;

[0298]FIG. 18 is an X-ray diffraction spectrum of a reaction productobtained in Example 27;

[0299]FIG. 19 is an X-ray diffraction spectrum of a reaction productobtained in Example 28;

[0300]FIG. 20 is an X-ray diffraction spectrum of a reaction productobtained in Example 29;

[0301]FIG. 21 is an X-ray diffraction spectrum of a reaction productobtained in Example 30;

[0302]FIG. 22 is an X-ray diffraction spectrum of a reaction productobtained in Example 31;

[0303]FIG. 23 is an X-ray diffraction spectrum of a reaction productobtained in Example 32;

[0304]FIG. 24 is an X-ray diffraction spectrum of a reaction productobtained in Example 33;

[0305]FIG. 25 is an X-ray diffraction spectrum of a reaction productobtained in Comparative Example;

[0306]FIG. 26 is a mass spectrum;

[0307]FIG. 27 is an infrared absorption spectrum;

[0308]FIG. 28 is an X-ray diffraction spectrum of a reaction productobtained in Example 34;

[0309]FIG. 29 is an infrared absorption spectrum;

[0310]FIG. 30 is an infrared absorption spectrum;

[0311]FIG. 31 is a light absorption spectrum;

[0312]FIG. 32 is a light absorption spectrum of a solution;

[0313]FIG. 33 is an infrared absorption spectrum;

[0314]FIG. 34 is an infrared absorption spectrum; and

[0315]FIG. 35 is an infrared absorption spectrum.

What is claimed is:
 1. A crystalline reaction product having chargegenerating properties and capable of being obtained by reacting anitrile derivative of the general formula (1) with a phthalonitrilederivative of the general formula (2):

wherein R₁-R₅ stand, independently from each other, for a hydrogen atom,a halogen atom, an aliphatic hydrocarbyl group which may have asubstituent, an aromatic group which may have a substituent, ahydrocarbyloxy group which may have a substituent, a nitro group or acyano group and n is an integer of 1 or 2, with the proviso that two ofR₂-R₅ may link to each other to form a ring.
 2. A crystalline reactionproduct having charge generating properties and capable of beingobtained by reacting a nitrile derivative of the general formula (1)with a phthalonitrile derivative of the general formula (2) and a metalor a metal compound:

wherein R₁-R₅ stand, independently from each other, for a hydrogen atom,a halogen atom, an aliphatic hydrocarbyl group which may have asubstituent, an aromatic group which may have a substituent, ahydrocarbyloxy group which may have a substituent, a nitro group or acyano group and n is an integer of 1 or 2, with the proviso that two ofR₂-R₅ may link to each other to form a ring.
 3. A crystalline reactionproduct having charge generating properties and capable of beingobtained by reacting a nitrile derivative of the general formula (1)with a 1,3-diiminoisoindoline derivative of the general formula (3):

wherein R₁-R₅ stand, independently from each other, for a hydrogen atom,a halogen atom, an aliphatic hydrocarbyl group which may have asubstituent, an aromatic group which may have a substituent, ahydrocarbyloxy group which may have a substituent, a nitro group or acyano group and n is an integer of 1 or 2, with the proviso that two ofR₂-R₅ may link to each other to form a ring.
 4. A crystalline reactionproduct having charge generating properties and capable of beingobtained by reacting a nitrile derivative of the general formula (1)with a 1,3-diiminoisoindoline derivative of the general formula (3) anda metal or a metal compound:

wherein R₁-R₅ stand, independently from each other, for a hydrogen atom,a halogen atom, an aliphatic hydrocarbyl group which may have asubstituent, an aromatic group which may have a substituent, ahydrocarbyloxy group which may have a substituent, a nitro group or acyano group and n is an integer of 1 or 2, with the proviso that two ofR₂-R₅ may link to each other to form a ring.
 5. A reaction product asclaimed in any one of claims 1-4, characterized in that said reactionproduct has light absorption in 500-700 nm in a film spectrum.
 6. Areaction product as claimed in claim 2, characterized in that said metalis titanium.
 7. A reaction product as claimed in claim 2, characterizedin that said metal compound is a titanium compound.
 8. A reactionproduct as claimed in claim 4, characterized in that said metal istitanium.
 9. A reaction product as claimed in claim 4, characterized inthat said metal compound is a titanium compound.
 10. A reaction productas claimed in claim 6 or 7, characterized in that said reaction producthas a peak at a molecular weight of 1383±1 in mass spectrometry.
 11. Areaction product as claimed in any one of claims 6-10, characterized inthat elementary analysis by fluorescent X-ray spectroscopy shows Ti as ametal.
 12. A reaction product as claimed in any one of claims 1-11,characterized in that said reaction product has a strong diffractionpeak at a Bragg angle 2θ±0.2° of in the range of 20°-30° in a CuK_(α)X-ray diffraction pattern thereof.
 13. A reaction product as claimed inany one of claims 1-12, characterized in that said reaction product hasa strong diffraction peak at a Bragg angle 2θ±0.2° of 27.2° in a CuK_(α)X-ray diffraction pattern thereof.
 14. A reaction product as claimed inclaim 13, characterized in that said reaction product has no diffractionpeak at a Bragg angle 2θ±0.2° of in the range of 4°-10° in aCuK_(α)X-ray diffraction pattern thereof.
 15. A reaction product asclaimed in claim 13, characterized in that said reaction product has adiffraction peak at a Bragg angle 2θ±0.2° of in the range of 4°-10° in aCuK_(α), X-ray diffraction pattern thereof.
 16. An amorphous reactionproduct capable of being obtained by reacting a nitrile derivative ofthe general formula (1) with a phthalonitrile derivative of the generalformula (2):

wherein R₁-R₅ stand, independently from each other, for a hydrogen atom,a halogen atom, an aliphatic hydrocarbyl group which may have asubstituent, an aromatic group which may have a substituent, ahydrocarbyloxy group which may have a substituent, a nitro group or acyano group and n is an integer of 1 or 2, with the proviso that two ofR₂-R₅ may link to each other to form a ring.
 17. An amorphous reactionproduct capable of being obtained by reacting a nitrile derivative ofthe general formula (1) with a phthalonitrile derivative of the generalformula (2) and a metal or a metal compound:

wherein R₁-R₅ stand, independently from each other, for a hydrogen atom,a halogen atom, an aliphatic hydrocarbyl group which may have asubstituent, an aromatic group which may have a substituent, ahydrocarbyloxy group which may have a substituent, a nitro group or acyano group and n is an integer of 1 or 2, with the proviso that two ofR₂-R₅ may link to each other to form a ring.
 18. An amorphous reactionproduct capable of being obtained by reacting a nitrile derivative ofthe general formula (1) with a 1,3-diiminoisoindoline derivative of thegeneral formula (3):

wherein R₁-R₅ stand, independently from each other, for a hydrogen atom,a halogen atom, an aliphatic hydrocarbyl group which may have asubstituent, an aromatic group which may have a substituent, ahydrocarbyloxy group which may have a substituent, a nitro group or acyano group and n is an integer of 1 or 2, with the proviso that two ofR₂-R₅ may link to each other to form a ring.
 19. An amorphous reactionproduct capable of being obtained by reacting a nitrile derivative ofthe general formula (1) with a 1,3-diiminoisoindoline derivative of thegeneral formula (3) and a metal or a metal compound:

wherein R₁-R₅ stand, independently from each other, for a hydrogen atom,a halogen atom, an aliphatic hydrocarbyl group which may have asubstituent, an aromatic group which may have a substituent, ahydrocarbyloxy group which may have a substituent, a nitro group or acyano group and n is an integer of 1 or 2, with the proviso that two ofR₂-R₅ may link to each other to form a ring.
 20. A process for theproduction of a product according to claim 14, characterized in that areaction product as recited in claim 15 is subjected to a crystalconverting treatment using at least one solvent selected from the groupconsisting of an organic solvent, an acid and water.
 21. A process forthe production of a product according to claim 14, characterized in thata reaction product as recited in any one of claims 16-19 is subjected toa crystal converting treatment using at least one solvent selected fromthe group consisting of an organic solvent, an acid and water.
 22. Apigment characterized by comprising a reaction product as recited in anyone of claims 1-15.
 23. An electrophotographic photoconductor comprisingan electroconductive support and a photoconductive layer providedthereon, characterized in that said photoconductive layer contains apigment as recited in claim
 22. 24. An electrophotographicphotoconductor as claimed in claim 23, characterized in that saidphotoconductive layer comprises a charge generation layer comprising acharge generating substance and a charge transport layer comprising acharge transporting substance and in that said pigment is contained insaid charge generation layer.
 25. A negatively charged typeelectrophotographic photoconductor as claimed in claim 24, characterizedin that said charge transporting substance is a positive hole transportsubstance and in that said charge generation layer and said chargetransport layer are provided on said support in this order.
 26. Anelectrophotographic photoconductor as claimed in claim 25, characterizedin that said positive hole transport substance is a stilbene compoundrepresented by the following formula (4):

wherein r₁ and r₂ stand, independently from each other, for asubstituted or unsubstituted alkyl group or a substituted orunsubstituted aryl group, r₃ and r₄ stand, independently from eachother, for a hydrogen atom, a substituted or unsubstituted alkyl group,a substituted or unsubstituted aryl group, or a hyterocyclic group, withthe proviso that r₁ and r₂ may together form a ring, and Ar₁ stands fora substituted or unsubstituted aryl group or a hyterocyclic group.
 27. Apositively charged type electrophotographic photoconductor as claimed inclaim 24, characterized in that said charge generation layer and saidcharge transport layer are provided on said support in this order. 28.An electrophotographic photoconductor as claimed in claim 27,characterized in that said electron transport substance is a2,3-diphenylindene compound represented by the following formula (5):

wherein R₁-R₄ stand, independently from each other, for a hydrogen atom,a halogen atom, a substituted or unsubstituted alkyl group, a cyanogroup or a nitro group, and A and B stand, independently from eachother, for a hydrogen atom, a halogen atom, a substituted orunsubstituted aryl group, a cyano group, an alkoxycarbonyl group or anaryloxycarbonyl group.
 29. An electrophotographic photoconductor asclaimed in claim 23, characterized in that said photoconductive layer isformed into a single layer.
 30. An electrophotographic machinecomprising charging means, exposing means, developing means, transfermeans, cleaning means, charge removing means and an electrophotographicphotoconductor, characterized in that an electrophotographicphotoconductor according to any one of claims 23-29 is provided as saidelectrophotographic photoconductor.
 31. A process cartridge for anelectrophotographic machine comprising charging means and anelectrophotographic photoconductor, characterized in that anelectrophotographic photoconductor according to any one of claims 23-29is provided as said electrophotographic photoconductor.